Constrained swelling of polymer networks: characterization of vapor-deposited cross-linked polymer thin films

Czech Academy of Sciences Publication Activity Database

Dušek, Karel; Choukourov, A.; Dušková-Smrčková, Miroslava; Biederman, H.

2014-01-01

Roč. 47, č. 13 (2014), s. 4417-4427 ISSN 0024-9297 R&D Projects: GA ČR GAP101/12/1306 Institutional support: RVO:61389013 Keywords : swelling * cross-linked polymer * elasticity Subject RIV: CD - Macromolecular Chemistry Impact factor: 5.800, year: 2014

Interpenetrating polymer networks based on polyol modified castor ...

Indian Academy of Sciences (India)

Interpenetrating polymer networks (IPNs) of glycerol modified castor oil polyurethane (GC–PU) and poly[2-hydroxyethylmethacrylate] (PHEMA) were synthesized using benzoyl peroxide as initiator and N,N-methylene bis acrylamide as crosslinker. GC–PU/PHEMA interpenetrating polymer networks were obtained by ...

Simulation of Stimuli-Responsive Polymer Networks

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Thomas Gruhn

2013-11-01

Full Text Available The structure and material properties of polymer networks can depend sensitively on changes in the environment. There is a great deal of progress in the development of stimuli-responsive hydrogels for applications like sensors, self-repairing materials or actuators. Biocompatible, smart hydrogels can be used for applications, such as controlled drug delivery and release, or for artificial muscles. Numerical studies have been performed on different length scales and levels of details. Macroscopic theories that describe the network systems with the help of continuous fields are suited to study effects like the stimuli-induced deformation of hydrogels on large scales. In this article, we discuss various macroscopic approaches and describe, in more detail, our phase field model, which allows the calculation of the hydrogel dynamics with the help of a free energy that considers physical and chemical impacts. On a mesoscopic level, polymer systems can be modeled with the help of the self-consistent field theory, which includes the interactions, connectivity, and the entropy of the polymer chains, and does not depend on constitutive equations. We present our recent extension of the method that allows the study of the formation of nano domains in reversibly crosslinked block copolymer networks. Molecular simulations of polymer networks allow the investigation of the behavior of specific systems on a microscopic scale. As an example for microscopic modeling of stimuli sensitive polymer networks, we present our Monte Carlo simulations of a filament network system with crosslinkers.

Flory-Stockmayer analysis on reprocessable polymer networks

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Li, Lingqiao; Chen, Xi; Jin, Kailong; Torkelson, John

Reprocessable polymer networks can undergo structure rearrangement through dynamic chemistries under proper conditions, making them a promising candidate for recyclable crosslinked materials, e.g. tires. This research field has been focusing on various chemistries. However, there has been lacking of an essential physical theory explaining the relationship between abundancy of dynamic linkages and reprocessability. Based on the classical Flory-Stockmayer analysis on network gelation, we developed a similar analysis on reprocessable polymer networks to quantitatively predict the critical condition for reprocessability. Our theory indicates that it is unnecessary for all bonds to be dynamic to make the resulting network reprocessable. As long as there is no percolated permanent network in the system, the material can fully rearrange. To experimentally validate our theory, we used a thiol-epoxy network model system with various dynamic linkage compositions. The stress relaxation behavior of resulting materials supports our theoretical prediction: only 50 % of linkages between crosslinks need to be dynamic for a tri-arm network to be reprocessable. Therefore, this analysis provides the first fundamental theoretical platform for designing and evaluating reprocessable polymer networks. We thank McCormick Research Catalyst Award Fund and ISEN cluster fellowship (L. L.) for funding support.

Process for crosslinking methylene-containing aromatic polymers with ionizing radiation

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Bell, Vernon L. (Inventor); Havens, Stephen J. (Inventor)

1990-01-01

A process for crosslinking aromatic polymers containing radiation-sensitive methylene groups (-CH2-) by exposing the polymers to ionizing radiation thereby causing crosslinking of the polymers through the methylene groups is described. Crosslinked polymers are resistant to most organic solvents such as acetone, alcohols, hydrocarbons, methylene, chloride, chloroform, and other halogenated hydrocarbons, to common fuels and to hydraulic fluids in contrast to readily soluble uncrosslinked polymers. In addition, the degree of crosslinking of the polymers depends upon the percentage of the connecting groups which are methylene which ranges from 5 to 50 pct and preferably from 25 to 50 pct of the connecting groups, and is also controlled by the level of irradiation which ranges from 25 to 1000 Mrads and preferably from 25 to 250 Mrads. The temperature of the reaction conditions ranges from 25 to 200 C and preferably at or slightly above the glass transition temperature of the polymer. The crosslinked polymers are generally more resistant to degradation at elevated temperatures such as greater than 150 C, have a reduced tendency to creep under load, and show no significant embrittlement of parts fabricated from the polymers.

Lithium polymer cell assembled by in situ chemical cross-linking of ionic liquid electrolyte with phosphazene-based cross-linking agent

International Nuclear Information System (INIS)

Choi, Ji-Ae; Kang, Yongku; Kim, Dong-Won

2013-01-01

Highlights: ► Ionic liquid-based cross-linked gel polymer electrolytes were synthesized and their electrochemical properties were investigated. ► Lithium polymer cells with in situ cross-linked gel polymer electrolytes exhibited reversible cycling behavior with good capacity retention. ► The use of ionic liquid-based cross-linked gel polymer electrolytes significantly improved the thermal stability of the cells. -- Abstract: Ionic liquid-based cross-linked gel polymer electrolytes were prepared with a phosphazene-based cross-linking agent, and their electrochemical properties were investigated. Lithium polymer cells composed of lithium anode and LiCoO 2 cathode were assembled with ionic liquid-based cross-linked gel polymer electrolyte and their cycling performance was evaluated. The interfacial adhesion between the electrodes and the electrolyte by in situ chemical cross-linking resulted in stable capacity retention of the cell. A reduction in the ionic mobility in both the electrolyte and the electrode adversely affected discharge capacity and high rate performance of the cell. DSC studies demonstrated that the use of ionic liquid-based cross-linked gel polymer electrolytes provided a significant improvement in the thermal stability of the cell

Shaped articles of cross-linked fluorocarbon polymers

International Nuclear Information System (INIS)

Gotcher, A.J.; Germeraad, P.B.

1981-01-01

A process is described which comprises (1) contacting (a) a shaped article of a polymeric composition wherein the polymer is a fluorocarbon polymer having a melting point of at least 200 0 C, the article having a tensile strength of at least 3,000 psi, with (b) a fluid composition comprising a cross-linking agent, until the article contains at least 2.5% by weight of the cross-linking agent; and (2) irradiating the shaped article with ionising radiation to a dosage not exceeding 50 Mrads under conditions such that the composition is cross-linked sufficiently to impart thereto an M 100 value of at least 300 psi, while maintaining a tensile strength of at least 3000 psi, the shaped article containing a specified proportion of the cross-linking agent. (author)

Inter-crosslinking network gels having both shape memory and high ductility

Science.gov (United States)

Amano, Yoshitaka; Hidema, Ruri; Furukawa, Hidemitsu

2012-04-01

Medical treatment for injuries should be easy and quick in many accidents. Plasters or bandages are frequently used to wrap and fix injured parts. If plasters or bandages have additional smart functions, such as cooling, removability and repeatability, they will be much more useful and effective. Here we propose innovative biocompatible materials, that is, nontoxic high-strength shape-memory gels as novel smart medical materials. These smart gels were prepared from two monomers (DMAAm and SA), a polymer (HPC), and an inter-crosslinking agent (Karenz-MOI). In the synthesis of the gels, 1) a shape-memory copolymer network is made from the DMAAm and the SA, and 2) the copolymer and the HPC are crosslinked by the Karenz-MOI. Thus the crosslinking points are connected only between the different polymers. This is our original technique of developing a new network structure of gels, named Inter-Crosslinking Network (ICN). The ICN gels achieve high ductility, going up to 700% strain in tensile tests, while the ICN gels contain about 44% water. Moreover the SA has temperature dependence due to its crystallization properties; thus the ICN gels obtain shape memory properties and are named ICN-SMG. While the Young's modulus of the ICN-SMG is large below their crystallization temperature and the gels behave like plastic materials, the modulus becomes smaller above the temperature and the gels turn back to their original shape.

Design and Application of Nanogel-Based Polymer Networks

Science.gov (United States)

Dailing, Eric Alan

Crosslinked polymer networks have wide application in biomaterials, from soft hydrogel scaffolds for cell culture and tissue engineering to glassy, high modulus dental restoratives. Composite materials formed with nanogels as a means for tuning network structure on the nanoscale have been reported, but no investigation into nanogels as the primary network component has been explored to this point. This thesis was dedicated to studying network formation from the direct polymerization of nanogels and investigating applications for these unique materials. Covalently crosslinked polymer networks were synthesized from polymerizable nanogels without the use of reactive small monomers or oligomers. Network properties were controlled by the chemical and physical properties of the nanogel, allowing for materials to be designed from nanostructured macromolecular precursors. Nanogels were synthesized from a thermally initiated solution free radical polymerization of a monomethacrylate, a dimethacrylate, and a thiol-based chain transfer agent. Monomers with a range of hydrophilic and hydrophobic character were copolymerized, and polymerizable groups were introduced through an alcohol-isocyanate click reaction. Nanogels were dispersible in water up to 75 wt%, including nanogels that contained a relatively high fraction of a conventionally water-insoluble component. Nanogels with molecular weights that ranged from 10's to 100's of kDa and hydrodynamic radii between 4 and 10 nm were obtained. Macroscopic crosslinked polymer networks were synthesized from the photopolymerization of methacrylate-functionalized nanogels in inert solvent, which was typically water. The nanogel composition and internal branching density affected both covalent and non-covalent interparticle interactions, which dictated the final mechanical properties of the networks. Nanogels with progressively disparate hydrophilic and hydrophobic character were synthesized to explore the potential for creating

Photo-induced Mass Transport through Polymer Networks

Science.gov (United States)

Meng, Yuan; Anthamatten, Mitchell

2014-03-01

Among adaptable materials, photo-responsive polymers are especially attractive as they allow for spatiotemporal stimuli and response. We have recently developed a macromolecular network capable of photo-induced mass transport of covalently bound species. The system comprises of crosslinked chains that form an elastic network and photosensitive fluorescent arms that become mobile upon irradiation. We form loosely crosslinked polymer networks by Michael-Addition between multifunctional thiols and small molecule containing acrylate end-groups. The arms are connected to the network by allyl sulfide, that undergoes addition-fragmentation chain transfer (AFCT) in the presence of free radicals, releasing diffusible fluorophore. The networks are loaded with photoinitiator to allow for spatial modulation of the AFCT reactions. FRAP experiments within bulk elastomers are conducted to establish correlations between the fluorophore's diffusion coefficient and experimental variables such as network architecture, temperature and UV intensity. Photo-induced mass transport between two contacted films is demonstrated, and release of fluorophore into a solvent is investigated. Spatial and temporal control of mass transport could benefit drug release, printing, and sensing applications.

Rational design of molecularly imprinted polymer: the choice of cross-linker.

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Muhammad, Turghun; Nur, Zohre; Piletska, Elena V; Yimit, Osmanjan; Piletsky, Sergey A

2012-06-07

The paper describes a rational approach for the selection of cross-linkers during the development of molecularly imprinted polymers (MIPs). As a model system for this research MIPs specific for the drug zidovudine (AZT) were designed and tested. Three cross-linkers trimethylolpropane trimethacrylate (TRIM), ethylene glycol dimethacrylate (EGDMA) and divinylbenzene (DVB) were studied. The analogue of zidovudine (AZT) ester (AZT-ES) was used as a dummy template. The imprinting factors for all of the polymers in the static adsorption experiments were calculated. The data on the AZT adsorption by control polymers (CP), which were prepared with different cross-linkers without a functional monomer, was also analyzed. DVB was found to be more inert towards zidovudine than EGDMA and TRIM, which was confirmed by both molecular modelling and adsorption experiments. It was demonstrated that DVB-based polymers had a higher imprinting factor (I = 1.85) compared with other tested cross-linked polymers. It was suggested that the selection of the cross-linker should be based on the strength of the interaction with the template: the cross-linker which displays lower binding of the template should be preferential because it generates MIPs with lower non-specific binding and a higher imprinting factor, and therefore specificity. Which cross-linker to use for the preparation of any particular MIP can be determined by analysis of the interactions between the cross-linker and template. This could be done either virtually using computational modelling or by template adsorption using a small library of polymers prepared using different cross-linkers.

Effect of pH on chitosan hydrogel polymer network structure.

Science.gov (United States)

Xu, Hongcheng; Matysiak, Silvina

2017-06-29

Chitosan is a molecule that can form water-filled 3D polymer networks with a wide range of applications. A new coarse-grained model for chitosan hydrogel was developed to explore its pH-dependent self-assembly behavior and mechanical properties. Our results indicate that the underlying polymer physical crosslinking pattern induced by solution pH has a significant effect on hydrogel elastic moduli. With this model, we obtain pH-dependent structural and mechanical property changes in agreement with experimental observations, and provide a molecular mechanism behind the changes in polymer crosslinking patterns.

The effect of chain flexibility and chain mobility on radiation crosslinking reactions of polymers

International Nuclear Information System (INIS)

Sun Jiazhen

2003-01-01

Flexibility of polymer chains is an important factor to effects of radiation crosslinking of the polymer. Polymers with flexible chains are easier to be crosslinked, with lower dose of gelation, than polymers with more rigid chains. And it is known that most polymers with abnormal rigidity can be radiation-crosslinked only at high temperatures when the molecular chains get enough mobility. The flexibility of polymer chains also influences the relationship between degree of degradation and radiation dose. A chain flexibility factor β has been introduced to modify the Charlesby-Pinner equation of sol-fraction and radiation dose. The new relationship equation applies to a wider range of polymers in radiation crosslinking. Studies also show that for flexible polymers with lower T g and molecular internal rotating factor, mechanism of radiation crosslinking is mainly in H type, whereas for rigid polymers with higher T g and molecular internal rotating factor, mechanism of radiation crosslinking is mainly in T type

Radiation crosslinking of polymer materials and its functional properties

International Nuclear Information System (INIS)

Yoshii, Fumio

2006-01-01

It was found out that radiation crosslinking of biodegradable polymer such as poly (butylene succinate, PBS) and poly(ε-caprolactone, PCL) could be achieved by radiation in the presence of small amount of trimethallyl isocyanurate (TMAIC) or 1% triallyl isocyanurate (TAIC). Such modification is very effective to improve heat resistance for PBS and PCL. Poly (lactic acid, PLA) undergoes crosslinking effectively with 3% TAIC by radiation. Outstanding feature of these polymers is their biodegradability even after crosslinking. Radiation crosslinking of polysaccharide derivatives such as carboxymethyl-cellulose (CMC) is also achieved in aqueous solution at high concentration (paste-like state). The crosslinking behavior was largely affected by the degree of substitution (DS) and polymer concentration. After removal of water the dry CMC gel is used as water absorbent material. This dry gel is the most effective for removal of large amounts of water from organic wastes, resulting in the acceleration of their fermentation. Measurement of swelling ratio of the dry CMC gel in 0.9% NaCl aqueous solution was carried out to expand application fields for this material. Radiation crosslinked poly (vinyl alcohol) hydrogel was successfully commercialized from July 2004 as wound dressing for accelerated healing. Furthermore, this material was also used as gel protector to prevent shore sore and was further commercialized. (author)

A colourimetric method for the determination of the degree of chemical cross-linking in aspartic acid-based polymer gels

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B. Gyarmati

2015-02-01

Full Text Available A 2,4,6-trinitrobenzenesulphonic acid (TNBS-based assay is developed to determine the degree of chemical cross-linking in aspartic acid-based polymer gels. The conventional colourimetric method for the quantitative determination of amine groups is difficult to use in polymer networks; thus, an improved method is developed to analyse polymer gels swollen in dimethyl sulfoxide (DMSO. Reaction products of the derivatizing reaction are examined by NMR. The chemical stability of the reagent is increased in DMSO, and the method shows satisfactory linearity and accuracy. The degree of chemical cross-linking in the investigated gels is close to its theoretical maximum, but the conversion of the pendant amine groups to cross-linking points is strongly dependent on the feed composition of the gels.

Ductile thermoset polymers via controlling network flexibility.

Science.gov (United States)

Hameed, N; Salim, N V; Walsh, T R; Wiggins, J S; Ajayan, P M; Fox, B L

2015-06-18

We report the design and synthesis of a polymer structure from a cross-linkable epoxy-ionic liquid system which behaves like a hard and brittle epoxy thermoset, perfectly ductile thermoplastic and an elastomer, all depending on controllable network compositions.

Grafting of Interpenetrating Networks of Two Stimuli-responsive Polymers onto PP

International Nuclear Information System (INIS)

Ruiz, J. C.

2006-01-01

In this work a new strategy was used to prepare interpenetrating polymer networks (IPNs) of two 'stimuli-responsive' polymers: a thermosensitive poly N-isopropylacrylamide (PNIPAAm) and pH sensitive poly acrylic acid (PAAc), the last grafted onto PP films. IPNs are a combination of two or more polymers in network form, which are mixed together (not chemically but physically), with al least one such polymer polymerized and/or crosslinked in the immediate presence of the other(s). The 'stimuli-responsive' polymers, also called 'smart' polymers, exhibit relatively large and sharp physical or chemical changes in response to small physical or chemical stimuli. These polymers are being used as hydrogels or copolymers for technical applications in chemical and mechanical engineering systems such as mass separation, chemical valves, temperature or pH indicators, biomedical and drug delivery systems. For these applications a rapid response and good mechanical properties are necessary. Formerly when PNIPAAm and PAAc were chemically combined their sensitivity was often altered or eliminated and their copolymer had poor mechanical properties. Attempts to solve this problem by creating IPN's with a reduced gel size or by using a macro-porous structure were successful in preserving sensitivity but failed to produce adequate mechanical properties. The object of this paper is to improve the past results of using a binary graft of PNIPAAm and PAAc onto poly(tetrafluoroethylene) PTFE. Poly acrylic acid was grafted onto polypropylene films (with good mechanical properties) by gamma radiation in air (pre-irradiation method), then these grafts were crosslinked using any of the next two methods: The first one, the grafted film in water and argon atmosphere by gamma radiation; and the second one, in the same conditions, but adding a crosslinking agent N, N'-methylenebisacrylamide (MBAAm). The second network was carried out in situ, in the cross-linked PAAc grafted onto PP films, by

Formation of interfacial network structure via photo-crosslinking in carbon fiber/epoxy composites

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S. H. Deng

2014-07-01

Full Text Available A series of diblock copolymers (poly(n-butylacrylate-co-poly(2-hydroxyethyl acrylate-b-poly(glycidyl methacrylate ((PnBA-co-PHEA-b-PGMA, containing a random copolymer block PnBA-co-PHEA, were successfully synthesized by atom transfer radical polymerization (ATRP. After being chemically grafted onto carbon fibers, the photosensitive methacrylic groups were introduced into the random copolymer, giving a series of copolymers (poly(n-butylacrylate-co-poly(2-methacryloyloxyethyl acrylate-b-poly(glycidyl methacrylate((PnBA-co-PMEA-b-PGMA. Dynamic mechanical analysis indicated that the random copolymer block after ultraviolet (UV irradiation was a lightly crosslinked polymer and acted as an elastomer, forming a photo-crosslinked network structure at the interface of carbon fiber/epoxy composites. Microbond test showed that such an interfacial network structure greatly improved the cohesive strength and effectively controlled the deformation ability of the flexible interlayer. Furthermore, three kinds of interfacial network structures, i physical crosslinking by H-bonds, ii chemical crosslinking by photopolymerization, and iii interpenetrating crosslinked network by photopolymerization and epoxy curing reaction were received in carbon fiber/epoxy composite, depending on the various preparation processes.

Pressure effects on the crosslinking by gamma radiation of commercial vinil polymers

International Nuclear Information System (INIS)

Lopez V, D.; Burillo, G.

1991-01-01

Gamma-ray induced crosslinking of some commercial polymers was investigated. Polypropylene, polystyrene, polyvinilchloride, polyacrylamide and polyvinilalcohol were compressed to disks and the effect to pressure on the crosslinking was studied. In all the cases, the crosslinking yield increased significantly by compressing the polymers. This is probably because oxygen is removed from polymer by the effect of the pressure and therefore the chain scission is prevented. The effect of pressure is also due to the decrease in the intermolecular distance and thus the coupling of polymer radicals is facilitated. (Author)

Recyclable Cu(II)-Coordination Crosslinked Poly(benzimidazolyl pyridine)s as High-Performance Polymers.

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Wang, Cheng; Yang, Li; Chang, Guanjun

2018-03-01

Crosslinked high-performance polymers have many industrial applications, but are difficult to recycle or rework. A novel class of recyclable crosslinking Cu(II)-metallo-supramolecular coordination polymers are successfully prepared, which possess outstanding thermal stability and mechanical property. More importantly, the Cu 2+ coordination interactions can be further removed via external pyrophosphate to recover the linear polymers, which endow the crosslinking polymers with recyclability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Molecular Dynamics Study of Crosslinked Phthalonitrile Polymers: The Effect of Crosslink Density on Thermomechanical and Dielectric Properties

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Janel Chua

2018-01-01

Full Text Available In this work, molecular dynamics (MD and molecular mechanics (MM simulations are used to study well-equilibrated models of 4,4′-bis(3,4-dicyanophenoxybiphenyl (BPh–1,3-bis(3-aminophenoxybenzene (m-APB phthalonitrile (PN system with a range of crosslink densities. A cross-linking technique is introduced to build a series of systems with different crosslink densities; several key properties of this material, including thermal expansion, mechanical properties and dielectric properties are studied and compared with experimental results. It is found that the coefficient of linear thermal expansion predicted by the model is in good agreement with experimental results and indicative of the good thermal stability of the PN polymeric system. The simulation also shows that this polymer has excellent mechanical property, whose strength increases with increasing crosslink density. Lastly and most importantly, the calculated dielectric constant—which shows that this polymer is an excellent insulating material—indicates that there is an inverse relation between cross-linking density and dielectric constant. The trend gave rise to an empirical quadratic function which can be used to predict the limits of attainable dielectric constant for highly crosslinked polymer systems. The current computational work provides strong evidence that this polymer is a promising material for aerospace applications and offers guidance for experimental studies of the effect of cross-linking density on the thermal, mechanical and dielectric properties of the material.

Radiation cross-linked polymers: Recent developments and new applications

International Nuclear Information System (INIS)

Rouif, Sophie

2005-01-01

The purpose of the present paper is to review the innovative and recent applications of radiation cross-linking of polymers that reinforces their dimensional stability in chemically aggressive and high temperature conditions. Radiation cross-linking can be applied to a great number of plastics: thermoplastics, elastomers and thermoplastic elastomers (TPE). Some of them can cross-link on their own, some others need to be formulated with a cross-linking agent (promoter) or to be modified during their polymerization. Some results of chemical and thermomechanical characterizations of radiation cross-linked plastics based on engineering polymers will be described, and their advantages will be emphasized in relation with their applications in various sectors: pipes and cables, packaging, automotive, electrical engineering and electronics, including connectors, surface mounted devices, integrated circuits, 3D-MID technology, etc. The paper will conclude with a short review of the industrial irradiation facilities (EB facilities and gamma plants) adapted to the treatment of such various products

Swelling of cross-linked polymers: interpretations and misinterpretations

Czech Academy of Sciences Publication Activity Database

Dušek, Karel; Dušková-Smrčková, Miroslava

2017-01-01

Roč. 254, 20 August (2017), s. 102 ISSN 0065-7727. [ACS National Meeting & Exposition /254./. 20.08.2017-24.08.2017, Washington] Institutional support: RVO:61389013 Keywords : swelling * cross-linked polymer Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science

Cross-Linked Solid Polymer Electrolyte for All-Solid-State Rechargeable Lithium Batteries

International Nuclear Information System (INIS)

Ben youcef, Hicham; Garcia-Calvo, Oihane; Lago, Nerea; Devaraj, Shanmukaraj; Armand, Michel

2016-01-01

Semi-interpenetrated network Solid Polymer Electrolytes (SPEs) were fabricated by UV-induced cross-linking of poly(ethyleneglycol) diacrylate (PEGDA) and divinylbenzene (DVB) within a poly(ethyleneoxide) (PEO) matrix (M v = 5 × 10 6 g mol −1 ), comprising lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI), at a molar ratio of EO:Li ∼ 30:1. The influence of the DVB content on the final SPE properties was investigated in detail. An increase of DVB concentration resulted in self-standing polymer electrolytes. The DVB cross-linker incorporation was found to decrease the crystallinity of the PEO matrix from 34% to 23%, with a decrease in the melting temperature (T m ) of the membrane from 50 °C to 34 °C. Moreover, the influence of the DVB concentration on the ionic conductivity was determined for polymer electrolytes with 0, 10, 20 and 45% DVB from room temperature (RT) to 80 °C. The resulting SPEs showed a high electrochemical stability of 4.3 V as well as practical conductivity values exceeding 10 −4 S cm −1 at 70 °C. Cycling performance of these semi-interpenetrated SPE’s have been shown with a Li metal polymer battery and all solid -state Li sulphur battery.

Studies of network structure and dynamics of e-beam crosslinked PVPs. From macro to nano

International Nuclear Information System (INIS)

Dispenza, C.; Grimaldi, N.; Sabatino, M.A.; Todaro, S.; Alessi, S.; Spadaro, G.; Bulone, D.; Giacomazza, D.; Przybytniak, G.

2011-01-01

Complete text of publication follows. Much interest has been paid to develop a variety of radiation-crosslinked hydrated polymeric materials, which swell in water but do not dissolve, as biocompatible materials used for wound healing, drug delivery system, surface-coating material for medically used devices, etc. With the aim of establishing design rules to produce hydrogels of controlled size at the nanoscale and desired internal network structure using conventional electron accelerators and set-ups, here we attempt a description in terms of structural and dynamic properties of polymer networks generated through e-beam irradiation of aqueous solutions of the same model polymer, a commercial grade poly(N-vinyl-pyrrolidone), subjected to e-beam irradiation with a 12 MeV Linac accelerator, at same dose (40 kGy) and dose-rate (100 kGy/h) and at the variance of polymer concentration in water. Concentration has been systematically varied from above (10, 8, 6, 4, 2% w) to below (1, 0.5, 0.25, 0.1, 0.05% w) the critical chain overlap concentration value (∼ 1% w) of the chosen polymer in water, as estimated by intrinsic viscosity measurements. The transition between macroscopic gelation and micro-/nanogels formation is observed just below the critical overlap concentration (0.5% w), whereas the net prevalence of intra-molecular over inter-molecular crosslinking occurs at a polymer concentration below 0.25% w, as revealed by both dynamic and static laser light scattering measurements. Significant structural differences between nanoscalar 'finite' crosslinked networks and macrogels are evidenced by both FTIR and solid state NMR spectra. Polymeric segments mobility of the formed networks, at the different scales, has been assessed through stress-rheometry, solid-state cross-polarization times and nuclear relaxation time NMR studies of the freeze-dried residues.

Role of special cross-links in structure formation of bacterial DNA polymer

Science.gov (United States)

Agarwal, Tejal; Manjunath, G. P.; Habib, Farhat; Lakshmi Vaddavalli, Pavana; Chatterji, Apratim

2018-01-01

Using data from contact maps of the DNA-polymer of Escherichia coli (E. Coli) (at kilobase pair resolution) as an input to our model, we introduce cross-links between monomers in a bead-spring model of a ring polymer at very specific points along the chain. Via suitable Monte Carlo simulations, we show that the presence of these cross-links leads to a particular organization of the chain at large (micron) length scales of the DNA. We also investigate the structure of a ring polymer with an equal number of cross-links at random positions along the chain. We find that though the polymer does get organized at the large length scales, the nature of the organization is quite different from the organization observed with cross-links at specific biologically determined positions. We used the contact map of E. Coli bacteria which has around 4.6 million base pairs in a single circular chromosome. In our coarse-grained flexible ring polymer model, we used 4642 monomer beads and observed that around 80 cross-links are enough to induce the large-scale organization of the molecule accounting for statistical fluctuations caused by thermal energy. The length of a DNA chain even of a simple bacterial cell such as E. Coli is much longer than typical proteins, hence we avoided methods used to tackle protein folding problems. We define new suitable quantities to identify the large scale structure of a polymer chain with a few cross-links.

Tunable photonic multilayer sensors from photo-crosslinkable polymers

Science.gov (United States)

Chiappelli, Maria; Hayward, Ryan

2014-03-01

The fabrication of tunable photonic multilayer sensors from stimuli-responsive, photo-crosslinkable polymers will be described. Benzophenone is covalently incorporated as a pendent photo-crosslinker, allowing for facile preparation of multilayer films by sequential spin-coating and crosslinking processes. Copolymer chemistries and layer thicknesses are selected to provide robust multilayer sensors which can show color changes across nearly the full visible spectrum due to the specific stimulus-responsive nature of the hydrated film stack. We will describe how this approach is extended to alternative sensor designs by tailoring the thickness and chemistry of each layer independently, allowing for the preparation of sensors which depend not only on the shift in wavelength of a reflectance peak, but also on the transition between Bragg mirrors and filters. Device design is optimized by photo-patterning sensor arrays on a single substrate, providing more efficient fabrication time as well as multi-functional sensors. Finally, radiation-sensitive multilayers, designed by choosing polymers which will preferentially degrade or crosslink under ionizing radiation, will also be described.

Cross-linked structure of network evolution

International Nuclear Information System (INIS)

Bassett, Danielle S.; Wymbs, Nicholas F.; Grafton, Scott T.; Porter, Mason A.; Mucha, Peter J.

2014-01-01

We study the temporal co-variation of network co-evolution via the cross-link structure of networks, for which we take advantage of the formalism of hypergraphs to map cross-link structures back to network nodes. We investigate two sets of temporal network data in detail. In a network of coupled nonlinear oscillators, hyperedges that consist of network edges with temporally co-varying weights uncover the driving co-evolution patterns of edge weight dynamics both within and between oscillator communities. In the human brain, networks that represent temporal changes in brain activity during learning exhibit early co-evolution that then settles down with practice. Subsequent decreases in hyperedge size are consistent with emergence of an autonomous subgraph whose dynamics no longer depends on other parts of the network. Our results on real and synthetic networks give a poignant demonstration of the ability of cross-link structure to uncover unexpected co-evolution attributes in both real and synthetic dynamical systems. This, in turn, illustrates the utility of analyzing cross-links for investigating the structure of temporal networks

Cross-linked structure of network evolution

Energy Technology Data Exchange (ETDEWEB)

Bassett, Danielle S., E-mail: dsb@seas.upenn.edu [Department of Bioengineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104 (United States); Department of Physics, University of California, Santa Barbara, California 93106 (United States); Sage Center for the Study of the Mind, University of California, Santa Barbara, California 93106 (United States); Wymbs, Nicholas F.; Grafton, Scott T. [Department of Psychology and UCSB Brain Imaging Center, University of California, Santa Barbara, California 93106 (United States); Porter, Mason A. [Oxford Centre for Industrial and Applied Mathematics, Mathematical Institute, University of Oxford, Oxford OX2 6GG (United Kingdom); CABDyN Complexity Centre, University of Oxford, Oxford, OX1 1HP (United Kingdom); Mucha, Peter J. [Carolina Center for Interdisciplinary Applied Mathematics, Department of Mathematics, University of North Carolina, Chapel Hill, North Carolina 27599 (United States); Department of Applied Physical Sciences, University of North Carolina, Chapel Hill, North Carolina 27599 (United States)

2014-03-15

We study the temporal co-variation of network co-evolution via the cross-link structure of networks, for which we take advantage of the formalism of hypergraphs to map cross-link structures back to network nodes. We investigate two sets of temporal network data in detail. In a network of coupled nonlinear oscillators, hyperedges that consist of network edges with temporally co-varying weights uncover the driving co-evolution patterns of edge weight dynamics both within and between oscillator communities. In the human brain, networks that represent temporal changes in brain activity during learning exhibit early co-evolution that then settles down with practice. Subsequent decreases in hyperedge size are consistent with emergence of an autonomous subgraph whose dynamics no longer depends on other parts of the network. Our results on real and synthetic networks give a poignant demonstration of the ability of cross-link structure to uncover unexpected co-evolution attributes in both real and synthetic dynamical systems. This, in turn, illustrates the utility of analyzing cross-links for investigating the structure of temporal networks.

Role of architecture in the elastic response of semiflexible polymer and fiber networks

Science.gov (United States)

Heussinger, Claus; Frey, Erwin

2007-01-01

We study the elasticity of cross-linked networks of thermally fluctuating stiff polymers. As compared to their purely mechanical counterparts, it is shown that these thermal networks have a qualitatively different elastic response. By accounting for the entropic origin of the single-polymer elasticity, the networks acquire a strong susceptibility to polydispersity and structural randomness that is completely absent in athermal models. In extensive numerical studies we systematically vary the architecture of the networks and identify a wealth of phenomena that clearly show the strong dependence of the emergent macroscopic moduli on the underlying mesoscopic network structure. In particular, we highlight the importance of the polymer length, which to a large extent controls the elastic response of the network, surprisingly, even in parameter regions where it does not enter the macroscopic moduli explicitly. Understanding these subtle effects is only possible by going beyond the conventional approach that considers the response of typical polymer segments only. Instead, we propose to describe the elasticity in terms of a typical polymer filament and the spatial distribution of cross-links along its backbone. We provide theoretical scaling arguments to relate the observed macroscopic elasticity to the physical mechanisms on the microscopic and mesoscopic scales.

Transformation of metal-organic framework to polymer gel by cross-linking the organic ligands preorganized in metal-organic framework.

Science.gov (United States)

Ishiwata, Takumi; Furukawa, Yuki; Sugikawa, Kouta; Kokado, Kenta; Sada, Kazuki

2013-04-10

Until now, seamless fusion of metal-organic frameworks (MOFs) and covalently cross-linked polymer gels (PG) at molecular level has been extremely rare, since these two matters have been regarded as opposite, that is, hard versus soft. In this report, we demonstrate transformation of cubic MOF crystals to PG via inner cross-linking of the organic linkers in the void space of MOF, followed by decomposition of the metal coordination. The obtained PG behaved as a polyelectrolyte gel, indicating the high content of ionic groups inside. Metal ions were well adsorbed in the PG due to its densely packed carboxylate groups. A chimera-type hybrid material consisting of MOF and PG was obtained by partial hydrolysis of resulting cross-linked MOF. The shape of resulting PG network well reflected the crystal structure of MOF employed as a template. Our results will connect the two different network materials that have been ever studied in the two different fields to provide new soft and hard hybrid materials, and the unique copolymerization in the large void space of the MOF will open a new horizon toward "ideal network polymers" never prepared before now.

Emerging synthetic strategies for core cross-linked star (CCS) polymers and applications as interfacial stabilizers: bridging linear polymers and nanoparticles.

Science.gov (United States)

Chen, Qijing; Cao, Xueteng; Xu, Yuanyuan; An, Zesheng

2013-10-01

Core cross-linked star (CCS) polymers become increasingly important in polymer science and are evaluated in many value-added applications. However, limitations exist to varied degrees for different synthetic methods. It is clear that improvement in synthetic efficiency is fundamental in driving this field moving even further. Here, the most recent advances are highlighted in synthetic strategies, including cross-linking with cross-linkers of low solubility, polymerization-induced self-assembly in aqueous-based heterogeneous media, and cross-linking via dynamic covalent bonds. The understanding of CCS polymers is also further refined to advocate their role as an intermediate between linear polymers and polymeric nanoparticles, and their use as interfacial stabilizers is rationalized within this context. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radiation induced estane polymer crosslinking

International Nuclear Information System (INIS)

Fletcher, M.; Foster, P.

1997-01-01

The exposure of polymeric materials to radiation has been known to induce the effects of crosslinking and degradation. The crosslinking phenomena comes about when two long chain polymers become linked together by a primary bond that extends the chain and increases the viscosity, molecular weight and the elastic modules of the polymer. This process has been observed in relatively short periods of time with fairly high doses of radiation, on the order of several megarads/hour. This paper address low dose exposure over long periods of time to determine what the radiation effects are on the polymeric binder material in PBX 9501. An experimental sample of binder material without explosives will be placed into a thermal and radiation field produced from a W-48 put mod 0. Another sample will be placed in a thermal environment without the radiation. The following is the test plan that was submitted to the Pantex process. The data presented here will be from the first few weeks of exposure and this test will be continued over the next few years. Subsequent data will hopefully be presented in the next compatibility and aging conference

Fabrication of polymer-alloy based on polytetrafluoroethylene by radiation-crosslinking

International Nuclear Information System (INIS)

Oshima, A.; Asano, S.; Hyunga, T.; Ichizuri, S.; Washio, M.

2003-01-01

Perfluoropolymer such as polytetrafluoroethylene (PTFE), tetrafluoroethylene co-perfluoroalkylvinylether (PFA) and tetrafluoroethylene-co-hexafluoropropylene (FFP) have been classified to be a typical polymer of radiation-induced degradation. However, we confirmed that the crosslinking of PTFE, PFA and FEP proceed by irradiation under selective condition where oxygen-free and high temperature above the melting temperature of them. In this study, fabrication of polymer-alloy based on PTFE has been demonstrated by radiation-crosslinking techniques. The polymer alloy, which was PTFE fine powder contained with other polymeric materials, was obtained by electron beams irradiation under oxygen-free atmosphere. Characterization of polymer-alloy based on PTFE has been studied by various measurements such as solid state 19F- and 13C-NMR spectroscopy, thermal analysis (DSC, TGA)

Simulations of tensile failure in glassy polymers: effect of cross-link density

International Nuclear Information System (INIS)

Panico, M; Narayanan, S; Brinson, L C

2010-01-01

Molecular dynamics simulations are adopted to investigate the failure mechanisms of glassy polymers, particularly with respect to increasing density of cross-links. In our simulations thermosetting polymers, which are cross-linked, exhibit an embrittlement compared with uncross-linked thermoplastics in a similar fashion to several experimental investigations (Levita et al 1991 J. Mater. Sci. 26 2348; Sambasivam et al 1997 J. Appl. Polym. Sci. 65 1001; Iijima et al 1992 Eur. Polym. J. 28 573). We perform a detailed analysis of this phenomenon and propose an interpretation based on the predominance of chain scission process over disentanglement in thermosetting polymers. We also elucidate the brittle fracture response of the thermosetting polymers

Ion pair reinforced semi-interpenetrating polymer network for direct methanol fuel cell applications.

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Fang, Chunliu; Julius, David; Tay, Siok Wei; Hong, Liang; Lee, Jim Yang

2012-06-07

This paper describes the synthesis of ion-pair-reinforced semi-interpenetrating polymer networks (SIPNs) as proton exchange membranes (PEMs) for the direct methanol fuel cells (DMFCs). Specifically, sulfonated poly(2,6-dimethyl-1,4-phenylene oxide) (SPPO), a linear polymer proton source, was immobilized in a brominated PPO (BPPO) network covalently cross-linked by ethylenediamine (EDA). The immobilization of SPPO in the SIPN network was accomplished not only by the usual means of mechanical interlocking but also by ion pair formation between the sulfonic acid groups of SPPO and the amine moieties formed during the cross-linking reaction of BPPO with EDA. Through the ion pair interactions, the immobilization of SPPO polymer in the BPPO network was made more effective, resulting in a greater uniformity of sulfonic acid cluster distribution in the membrane. The hydrophilic amine-containing cross-links also compensated for some of the decrease in proton conductivity caused by ion pair formation. The SIPN membranes prepared as such showed good proton conductivity, low methanol permeability, good mechanical properties, and dimensional stability. Consequently, the PPO based SIPN membranes were able to deliver a higher maximum power density than Nafion, demonstrating the potential of the SIPN structure for PEM designs.

Porous Cross-Linked Polyimide-Urea Networks

Science.gov (United States)

Meador, Mary Ann B. (Inventor); Nguyen, Baochau N. (Inventor)

2015-01-01

Porous cross-linked polyimide-urea networks are provided. The networks comprise a subunit comprising two anhydride end-capped polyamic acid oligomers in direct connection via a urea linkage. The oligomers (a) each comprise a repeating unit of a dianhydride and a diamine and a terminal anhydride group and (b) are formulated with 2 to 15 of the repeating units. The subunit was formed by reaction of the diamine and a diisocyanate to form a diamine-urea linkage-diamine group, followed by reaction of the diamine-urea linkage-diamine group with the dianhydride and the diamine to form the subunit. The subunit has been cross-linked via a cross-linking agent, comprising three or more amine groups, at a balanced stoichiometry of the amine groups to the terminal anhydride groups. The subunit has been chemically imidized to yield the porous cross-linked polyimide-urea network. Also provided are wet gels, aerogels, and thin films comprising the networks, and methods of making the networks.

Characterisation of radiation crosslinked polydimethylsiloxane

International Nuclear Information System (INIS)

Preston, C.M.L.; Hill, D.J.T.; Pomery, P.J.; Whittaker, A.K.

1998-01-01

Polysiloxanes, or silicones, are used widely in industry, as lubricants and process additives, as well as in many household products. The most common of the silicones is polydimethylsiloxane (PDMS). The fact that silicones crosslink during exposure to high energy radiation is well established. However, despite the number of studies performed on these systems, the exact mechanism of crosslinking has yet to be determined. Nuclear Magnetic Resonance spectroscopy (NMR) provides a useful method for the analysis of crosslinked polymer systems. Linear uncrosslinked PDMS is easily characterised in the solution state by NMR, as PDMS is readily soluble in common organic solvents. However, the onset of gelation caused by crosslinking results in an insoluble polymer network. The use of cross-polarisation (CP) and magic-angle spinning (MAS) in conjunction with high power decoupling has been shown to greatly enhance sensitivity of the NMR technique in solids. The true mechanism of crosslinking between polymer chains will be discussed

Radiation synthesis and characterisation of the network structure of natural/synthetic double-network superabsorbent polymers

International Nuclear Information System (INIS)

Şen, Murat; Hayrabolulu, Hande

2012-01-01

In this study radiation synthesis and characterisation of the network structure of acrylic acid sodium salt/locust bean gum, (AAcNa/LBG) natural/synthetic double-network super absorbent polymers were investigated. Quartet systems composed of acrylic acid sodium salt/locust bean gum/N,N methylene bis acrylamide/water (AAcNa/LBG/MBAAm/water) were prepared at varying degree of neutralisations (DN) by controlling the DN value of AAc and irradiated with gamma rays at ambient temperature at a very low dose rate. The influences of the DN on the swelling and network properties were examined. It was observed that the DN strongly affected the gelation and super absorption properties of the gels. Molecular weight between crosslinks (M ¯ c ), effective crosslink density (ν e ) and mesh size (ξ) of SAPs were calculated from swelling and shear modules data obtained from compression and oscillatory frequency sweep tests. M ¯ c values obtained from the uniaxial deformation experiments were very close to those obtained from the oscillatory shear experiments excluding the completely neutralised gel system. It was concluded that the uniaxial compression technique could be used for the characterisation of the network structure of a hydrogel as along with the rheological analyses; however, a very precise control of the gel size was also needed. - Highlights: ► Radiation synthesis and characterisation of AAcNa/LBG super absorbent polymers described. ► Influences of the DN on the swelling and network properties were examined. ► Molecular weight between crosslinks and effective crosslink density of SAPs were calculated. ► Suitability of rheology technique for the characterisation of hydrogels were demonstrated.

The role of unsaturations in the Gamma irradiation of crosslinkable polymers

International Nuclear Information System (INIS)

Satti, Angel J.; Ciolino, Andrés E.; Andreucetti, Noemí A.; Vallés, Enrique M.

2015-01-01

Nowadays, the understanding of the interaction of ionizing radiations with polymeric materials is becoming increasingly important. It is well known that many parameters regarding the synthesis of the polymers noticeably affect the irradiation process. In this work, an analysis of the effect of the type and the position of unsaturations in the molecular structure of crosslinkable polymers is performed. For such purpose, two solid semycristalline metallocenic ethylene 1-olefin copolymers (mEOC) which contain a low concentration of unsaturations from the synthesis, and their hydrogenated samples, were irradiated along with liquid poly(dimethylsiloxane) (PDMS) homo and copolymers containing different location and concentration of vinyl groups, which were structurally tailored through anionic synthesis. The source of irradiation was 60 Co, under vacuum at room temperature, in all the cases. The results indicated that terminal vinyls drastically accelerate the crosslinking to lower doses, even at much lower concentrations than other type and location of unsaturations for both, mEOC and PDMS, type of polymers. - Graphical abstract: Irradiated PEX # (ethylene copolymers with an # amount of 1-hexene -H- or 1-octadecene -OD) and their non-vinyl containing hidrogenated samples (PEX #h), along with irradiated vinyl functionalized siloxane polymers. Numbers within parentheses correspond to the number of vinyl groups per polymer chain for each irradiated polymer. Note that PDVi have been crosslinked with the lower dose of irradiation, although it has only one vinyl group. However, that is a terminal vinyl, while for the other polydimethylsiloxane derivatives, vinyls are within the main chain. - Highlights: • Terminal vinyls from metallocenic synthesis accelerate radioinduced crosslinking. • Trans vinyl structures are generated during irradiation, but vinyldenes are reluctant to react. • The position of the vinyl groups noticeably affects the irradiation process. �

Automobile parts by radiation crosslinking

International Nuclear Information System (INIS)

Yoshii, Fumio

2008-01-01

Radiation crosslinking, graft polymerization and degradation are useful technologies to improve polymer materials. The crosslinking causes improvement in strength, heat stability and processability to gives network structure for polymer materials and hence crosslinked materials are used in various fields, especially car parts. Electron beam (EB) of short time irradiation is used for these modifications. Irradiated (pre-vulcanized) before sulfur vulcanization rubber tires, heat resistant wires/cables, shrinkable tubes and foams of car parts are achieved by EB crosslinking. Polyethylene and polyvinyl chloride are used in cables and wires, polypropylene in plastic foams and natural rubber etc. In this paper radiation processing of tire, wire/cables, foams, shrinkable tubes and circuit protection devices (CPT) are explained. (author)

ROMP-based thermosetting polymers from modified castor oil with various cross-linking agents

Science.gov (United States)

Ding, Rui

Polymers derived from bio-renewable resources are finding an increase in global demand. In addition, polymers with distinctive functionalities are required in certain advanced fields, such as aerospace and civil engineering. In an attempt to meet both these needs, the goal of this work aims to develop a range of bio-based thermosetting matrix polymers for potential applications in multifunctional composites. Ring-opening metathesis polymerization (ROMP), which recently has been explored as a powerful method in polymer chemistry, was employed as a unique pathway to polymerize agricultural oil-based reactants. Specifically, a novel norbornyl-functionalized castor oil alcohol (NCA) was investigated to polymerize different cross-linking agents using ROMP. The effects of incorporating dicyclopentadiene (DCPD) and a norbornene-based crosslinker (CL) were systematically evaluated with respect to curing behavior and thermal mechanical properties of the polymers. Isothermal differential scanning calorimetry (DSC) was used to investigate the conversion during cure. Dynamic DSC scans at multiple heating rates revealed conversion-dependent activation energy by Ozawa-Flynn-Wall analysis. The glass transition temperature, storage modulus, and loss modulus for NCA/DCPD and NCA/CL copolymers with different cross-linking agent loading were compared using dynamic mechanical analysis. Cross-link density was examined to explain the very different dynamic mechanical behavior. Mechanical stress-strain curves were developed through tensile test, and thermal stability of the cross-linked polymers was evaluated by thermogravimetric analysis to further investigate the structure-property relationships in these systems.

Dynamic assembly of ultrasoft colloidal networks enables cell invasion within restrictive fibrillar polymers

Science.gov (United States)

Douglas, Alison M.; Fragkopoulos, Alexandros A.; Gaines, Michelle K.; Lyon, L. Andrew; Fernandez-Nieves, Alberto; Barker, Thomas H.

2017-01-01

In regenerative medicine, natural protein-based polymers offer enhanced endogenous bioactivity and potential for seamless integration with tissue, yet form weak hydrogels that lack the physical robustness required for surgical manipulation, making them difficult to apply in practice. The use of higher concentrations of protein, exogenous cross-linkers, and blending synthetic polymers has all been applied to form more mechanically robust networks. Each relies on generating a smaller network mesh size, which increases the elastic modulus and robustness, but critically inhibits cell spreading and migration, hampering tissue regeneration. Here we report two unique observations; first, that colloidal suspensions, at sufficiently high volume fraction (ϕ), dynamically assemble into a fully percolated 3D network within high-concentration protein polymers. Second, cells appear capable of leveraging these unique domains for highly efficient cell migration throughout the composite construct. In contrast to porogens, the particles in our system remain embedded within the bulk polymer, creating a network of particle-filled tunnels. Whereas this would normally physically restrict cell motility, when the particulate network is created using ultralow cross-linked microgels, the colloidal suspension displays viscous behavior on the same timescale as cell spreading and migration and thus enables efficient cell infiltration of the construct through the colloidal-filled tunnels.

Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

Science.gov (United States)

Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

2016-01-01

Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

Reprocessing and Recycling of Highly Cross-Linked Ion-Conducting Networks through Transalkylation Exchanges of C-N Bonds.

Science.gov (United States)

Obadia, Mona M; Mudraboyina, Bhanu P; Serghei, Anatoli; Montarnal, Damien; Drockenmuller, Eric

2015-05-13

Exploiting exchangeable covalent bonds as dynamic cross-links recently afforded a new class of polymer materials coined as vitrimers. These permanent networks are insoluble and infusible, but the network topology can be reshuffled at high temperatures, thus enabling glasslike plastic deformation and reprocessing without depolymerization. We disclose herein the development of functional and high-value ion-conducting vitrimers that take inspiration from poly(ionic liquid)s. Tunable networks with high ionic content are obtained by the solvent- and catalyst-free polyaddition of an α-azide-ω-alkyne monomer and simultaneous alkylation of the resulting poly(1,2,3-triazole)s with a series of difunctional cross-linking agents. Temperature-induced transalkylation exchanges of C-N bonds between 1,2,3-triazolium cross-links and halide-functionalized dangling chains enable recycling and reprocessing of these highly cross-linked permanent networks. They can also be recycled by depolymerization with specific solvents able to displace the transalkylation equilibrium, and they display a great potential for applications that require solid electrolytes with excellent mechanical performances and facile processing such as supercapacitors, batteries, fuel cells, and separation membranes.

Mesoscopic simulations of crosslinked polymer networks

NARCIS (Netherlands)

Megariotis, G.; Vogiatzis, G.G.; Schneider, L.; Müller, M.; Theodorou, D.N.

2016-01-01

A new methodology and the corresponding C++ code for mesoscopic simulations of elastomers are presented. The test system, crosslinked ds-1'4-polyisoprene' is simulated with a Brownian Dynamics/kinetic Monte Carlo algorithm as a dense liquid of soft, coarse-grained beads, each representing 5-10 Kuhn

Elasticity in Physically Cross-Linked Amyloid Fibril Networks

Science.gov (United States)

Cao, Yiping; Bolisetty, Sreenath; Adamcik, Jozef; Mezzenga, Raffaele

2018-04-01

We provide a constitutive model of semiflexible and rigid amyloid fibril networks by combining the affine thermal model of network elasticity with the Derjaguin-Landau-Vervey-Overbeek (DLVO) theory of electrostatically charged colloids. When compared to rheological experiments on β -lactoglobulin and lysozyme amyloid networks, this approach provides the correct scaling of elasticity versus both concentration (G ˜c2.2 and G ˜c2.5 for semiflexible and rigid fibrils, respectively) and ionic strength (G ˜I4.4 and G ˜I3.8 for β -lactoglobulin and lysozyme, independent from fibril flexibility). The pivotal role played by the screening salt is to reduce the electrostatic barrier among amyloid fibrils, converting labile physical entanglements into long-lived cross-links. This gives a power-law behavior of G with I having exponents significantly larger than in other semiflexible polymer networks (e.g., actin) and carrying DLVO traits specific to the individual amyloid fibrils.

Reorientational motion of a cross-link junction in a poly(dimethylsiloxane) network measured by time-resolved fluorescence depolarization

International Nuclear Information System (INIS)

Stein, A.D.; Hoffman, D.A.; Frank, C.W.; Fayer, M.D.

1992-01-01

The reorientational dynamics of a cross-link junction in poly(dimethylsiloxane) networks, measured by the fluorescence anisotropy decay of a chromophore tagged to the cross-link, have been investigated over a range of temperatures from T g +75 to T g +150. The probe chromophore, 1-dimethylamino-5-sulfonylnaphthalene amide (dansyl amide), is pendant to a trifunctional silane that acts as a cross-linking molecule. In cyclohexanol, the fluorescence anisotropy decay is in agreement with Debye--Stokes--Einstein hydrodynamic theory (rotational diffusion) demonstrating that the cross-linker can be used as a probe of orientational relaxation. The fluorescence anisotropy decays at a rapid rate in an end-linked poly(dimethyl siloxane) network reflecting fast reorientational motion of the cross-link junction. This reorientation appears diffusive and has a temperature dependence in accord with the Williams--Landel--Ferry equation. A model is proposed that suggests that reorientation and translational motion of the cross-link occur simultaneously and are both coupled to fluctuations of the polymer chain ends

The Effect of Filler-Polymer Interactions on Cold-Crystallization Kinetics in Crosslinked, Silica Filled PDMS/PDPS Copolymer Melts

International Nuclear Information System (INIS)

Chien, A; DeTeresa, S; Thompson, L; Cohenour, R; Balazs, B; Maxwell, R S

2006-01-01

Crystallization in a series of variable crosslink density poly(dimethyl-diphenyl) siloxanes random block copolymers reinforced through a mixture of precipitated and fumed silica fillers has been studied by Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), and X-ray Diffraction (XRD). The silicone composite studied was composed of 94.6 mol% Dimethoylsiloxane, 5.1 mol% diphenylsiloxane, and 0.3 mol% methyl-vinyl siloxane (which formed crosslinking after a peroxide cure). The polymer was filled with a mixture of 21.6 wt. % fumed silica and 4.0 wt. % precipitated silica previously treated with 6.8 wt. % ethoxy-endblocked siloxane processing aid. The base composite was characterized by a molecular weight between crosslinks in the polymer network of ∼24 kDa and an overall molecular weight (including the influence of the silica fillers) between crosslinks of ∼11 kDa. Molecular weight between crosslinks and filler-polymer interaction strength were then modified by exposure to γ-irradiation in either air or vacuum. The unirradiated material exhibited crystallization at -80 C as measured by DSC with a 16% crystallization as measured by XRD. Isothermal DMA experiments illustrated that crystallization at -85 C occurred over a 1.8 hour period in silica-filled systems and 2.2-2.6 hours in unfilled systems. The onset of crystallization typically occurred after a 30-minute incubation/nucleation period. The crystallization kinetics were dependent on crosslink density. Changes in molecular weight of a factor of two did not, however, change the amount of crystallization. Irradiation in vacuum resulted in faster overall crystallization rates compared to air irradiation for the same crosslink density, likely due to a reduction in the interaction between the polymer chains and the silica filler surface. Modulated differential scanning calorimetry contrasted the crystallization and melting behavior of pure PDMS versus the PDMS/PDPS base copolymer and helped

Removal of Parabens from Aqueous Solution Using β-Cyclodextrin Cross-Linked Polymer

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Mhd Radzi Bin Abas

2010-09-01

Full Text Available The removal of four parabens, methyl-, ethyl-, propyl-, and benzyl-paraben, by β-cyclodextrin (β-CD polymer from aqueous solution was studied. Different β-CD polymers were prepared by using two cross-linkers, i.e., hexamethylene diisocyanate (HMDI and toluene-2,6-diisocyanate (TDI, with various molar ratios of cross-linker. β-CD-HMDI polymer with molar ratio of 1:7 and β-CD-TDI polymer with ratio 1:4 gave the highest adsorption of parabens among the β-CD-HMDI and β-CD-TDI series, and were subsequently used for further studies. The adsorption capacity of β-CD-HMDI is 0.0305, 0.0376, 0.1854 and 0.3026 mmol/g for methyl-, ethyl-, propyl-, and benzyl-paraben, respectively. β-CD-TDI have higher adsorption capacities compared with β-CD-HMDI, the adsorption capacity are 0.1019, 0.1286, 0.2551, and 0.3699 mmol/g methyl-, ethyl-, propyl-, and benzyl-paraben respectively. The parameters studied were adsorption capacity, water retention, and reusability. Role of both cross-linker in adsorption, hydrophobicity of polymers, and adsorption capacity of different parabens were compared and discussed. All experiments were conducted in batch adsorption technique. These polymers were applied to real samples and showed positive results.

Crosslinkers of Different Types in Precipitation Polymerization of Acrylic Acid

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H. Eshaghi

2013-01-01

Full Text Available Crosslinked poly(acrylic acids were prepared using two types of crosslinker by precipitation polymerization method in a binary organic solvent. N,N’-methylenebisacrylamide (MBA and polyethylene glycol dimethacrylate (PEGDMA-330 were used as low-molecular weight and long-chain crosslinkers, respectively. The effect of various types of crosslinkers on polymer characteristics (i.e., gel content, equilibrium swelling, glass transition temperature, and rheological properties was investigated. Maximum amount of viscosity was obtained by using long-chain crosslinker. The Flory-Rehner equation and rubber elasticity theory were used to discuss the network structure of polymer. It was observed that, the glass transition temperature (Tg of the synthesized polymer containing PEGDMA-330 is higher than that of polymer containing MBA. Apparent and rotational viscosity were used to determine the optimal crosslinker type. In addition, the consistencycoefficient (m and flow behavior index (n parameter of Ostwald equation were investigated as well.

Depression of Glass Transition Temperatures of Polymer Networks by Diluents

NARCIS (Netherlands)

Brinke, Gerrit ten; Karasz, Frank E.; Ellis, Thomas S.

1983-01-01

A classical thermodynamic theory is used to derive expressions for the depression of the glass transition temperature Tg of a polymer network by a diluent. The enhanced sensitivity of Tg in cross-linked systems to small amounts of diluent is explained. Predictions of the theory are in satisfactory

The Effect of Double Crosslinker on Precipitation Polymerization of Poly(acrylic acid

Directory of Open Access Journals (Sweden)

Hajar Es-haghi

2014-06-01

Full Text Available Cross-linked poly(acrylic acids were prepared by dual cross-linkers via precipitation polymerization method in a binary organic solvent. Polyethylene glycol diacrylate (PEGDA-400 as a long-chain cross-linker and di(trimethylol propane tetraacrylate (DTMPTA as multifunctional cross-linker were used. PEGDA-400 was utilized to increase thickening properties and DTMPTA was used to improve the gel strength. The dual cross-linkers effect on the sample features (i.e., equilibrium swelling, thickening properties and rheological properties was investigated. Maximum amount of swelling was obtained by a high percentage of long-chain cross-linker. The apparent viscosity of the microgels was measured to determine their thickening properties for aqueous media. Maximum viscosity occurred at DT25-PE75 which was dependent on the type of cross-linkers in the polymer structure. The Flory-Rehner equation (from swelling ratio data and rubber elasticity theory (from rheometry data were used to discuss the network structure of the polymer. Increasing density of the network was shown by a sample containing high percentage of a four-functional cross-linker. The rheological properties of the cross-linked polymers were measured to determine storage modulus (strength network. The rheological behaviors demonstrated that the synthesized polymer containing a high amount of four-functional cross-linker had higher storage modulus (G′ than other samples. In addition the consistency coefficient (m and flow behavior index (n parameters of Ostwald equation were investigated as well. As a result, n values in each sample were found to be smaller than 1 and these results were fitted clearly with the pseudoplastic model. Apparent and rotational viscosities were used to determine the optimal cross-linker type (synthesized sample contained a high percentage of long-chain cross-linker.

Reorientational motion of a cross-link junction in a poly(dimethylsiloxane) network measured by time-resolved fluorescence depolarization

Energy Technology Data Exchange (ETDEWEB)

Stein, A.D. (Department of Chemistry, Stanford University, Stanford, California 94305 (United States)); Hoffman, D.A. (Department of Materials Science and Engineering, Stanford University, Stanford, California 94305 (United States)); Frank, C.W. (Department of Chemical Engineering, Stanford University, Stanford, California 94305 (United States)); Fayer, M.D. (Department of Chemistry, Stanford University, Stanford, California 94305 (United States))

1992-02-15

The reorientational dynamics of a cross-link junction in poly(dimethylsiloxane) networks, measured by the fluorescence anisotropy decay of a chromophore tagged to the cross-link, have been investigated over a range of temperatures from {ital T}{sub {ital g}}+75 to {ital T}{sub {ital g}}+150. The probe chromophore, 1-dimethylamino-5-sulfonylnaphthalene amide (dansyl amide), is pendant to a trifunctional silane that acts as a cross-linking molecule. In cyclohexanol, the fluorescence anisotropy decay is in agreement with Debye--Stokes--Einstein hydrodynamic theory (rotational diffusion) demonstrating that the cross-linker can be used as a probe of orientational relaxation. The fluorescence anisotropy decays at a rapid rate in an end-linked poly(dimethyl siloxane) network reflecting fast reorientational motion of the cross-link junction. This reorientation appears diffusive and has a temperature dependence in accord with the Williams--Landel--Ferry equation. A model is proposed that suggests that reorientation and translational motion of the cross-link occur simultaneously and are both coupled to fluctuations of the polymer chain ends.

Biomolecule-recognition gating membrane using biomolecular cross-linking and polymer phase transition.

Science.gov (United States)

Kuroki, Hidenori; Ito, Taichi; Ohashi, Hidenori; Tamaki, Takanori; Yamaguchi, Takeo

2011-12-15

We present for the first time a biomolecule-recognition gating system that responds to small signals of biomolecules by the cooperation of biorecognition cross-linking and polymer phase transition in nanosized pores. The biomolecule-recognition gating membrane immobilizes the stimuli-responsive polymer, including the biomolecule-recognition receptor, onto the pore surface of a porous membrane. The pore state (open/closed) of this gating membrane depends on the formation of specific biorecognition cross-linking in the pores: a specific biomolecule having multibinding sites can be recognized by several receptors and acts as the cross-linker of the grafted polymer, whereas a nonspecific molecule cannot. The pore state can be distinguished by a volume phase transition of the grafted polymer. In the present study, the principle of the proposed system is demonstrated using poly(N-isopropylacrylamide) as the stimuli-responsive polymer and avidin-biotin as a multibindable biomolecule-specific receptor. As a result of the selective response to the specific biomolecule, a clear permeability change of an order of magnitude was achieved. The principle is versatile and can be applied to many combinations of multibindable analyte-specific receptors, including antibody-antigen and lectin-sugar analogues. The new gating system can find wide application in the bioanalytical field and aid the design of novel biodevices.

Poly(vinylpyridine-co-styrene) based in situ cross-linked gel polymer electrolyte for lithium-ion polymer batteries

International Nuclear Information System (INIS)

Oh, Sijin; Kim, Dong Wook; Lee, Changjin; Lee, Myong-Hoon; Kang, Yongku

2011-01-01

A gel polymer electrolyte (GPE) was successfully prepared by means of an in situ cross-linking reaction of poly(2-vinylpyridine-co-styrene) and oligo(ethylene oxide) with epoxide functional groups at 65 °C without using a polymerization initiator. A stable gel polymer electrolyte could be obtained by adding only 1% of a polymer gelator. The ionic conductivity of the GPE containing 99 wt% of liquid electrolyte was measured to be ca. 10 −2 S/cm at the ambient temperature. The ionic conductivity of the resulting GPE was comparable to that of a pure liquid electrolyte. The electrochemical stability window of the prepared gel polymer electrolytes was measured to be 5.2 V. The test cell carried a discharge capacity of 133.2 mAh/g at 0.1 C and showed good cycling performance with negligible capacity fading after the 200th cycle, maintaining 99.5% coulombic efficiency throughout 200 cycles. The resulting gel polymer electrolyte prepared by in situ thermal cross-linking without a polymerization initiator holds promise for application to on the high power lithium-ion polymer batteries.

Creep-induced anisotropy in covalent adaptable network polymers.

Science.gov (United States)

Hanzon, Drew W; He, Xu; Yang, Hua; Shi, Qian; Yu, Kai

2017-10-11

Anisotropic polymers with aligned macromolecule chains exhibit directional strengthening of mechanical and physical properties. However, manipulating the orientation of polymer chains in a fully cured thermoset is almost impossible due to its permanently crosslinked nature. In this paper, we demonstrate that rearrangeable networks with bond exchange reactions (BERs) can be utilized to tailor the anisotropic mechanical properties of thermosetting polymers. When a constant force is maintained at BER activated temperatures, the malleable thermoset creeps in the direction of stress, and macromolecule chains align themselves in the same direction. The aligned polymer chains result in an anisotropic network with a stiffer mechanical behavior in the direction of creep, while with a more compliant behavior in the transverse direction. The degree of network anisotropy is proportional to the amount of creep strain. A multi-length scale constitutive model is developed to study the creep-induced anisotropy of thermosetting polymers. The model connects the micro-scale BER kinetics, orientation of polymer chains, and directional mechanical properties of network polymers. Without any fitting parameters, it is able to predict the evolution of creep strain at different temperatures and anisotropic stress-strain behaviors of CANs after creep. Predictions on the chain orientation are verified by molecular dynamics (MD) simulation. Based on parametric studies, it is shown that the influences of creep time and temperature on the network anisotropy can be generalized into a single parameter, and the evolution of directional modulus follows an Arrhenius type time-temperature superposition principle (TTSP). The presented work provides a facile approach to transform isotropic thermosets into anisotropic ones using simple heating, and their directional properties can be readily tailored by the processing conditions.

Desmosine-Inspired Cross-Linkers for Hyaluronan Hydrogels

Science.gov (United States)

Hagel, Valentin; Mateescu, Markus; Southan, Alexander; Wegner, Seraphine V.; Nuss, Isabell; Haraszti, Tamás; Kleinhans, Claudia; Schuh, Christian; Spatz, Joachim P.; Kluger, Petra J.; Bach, Monika; Tussetschläger, Stefan; Tovar, Günter E. M.; Laschat, Sabine; Boehm, Heike

2013-06-01

We designed bioinspired cross-linkers based on desmosine, the cross-linker in natural elastin, to prepare hydrogels with thiolated hyaluronic acid. These short, rigid cross-linkers are based on pyridinium salts (as in desmosine) and can connect two polymer backbones. Generally, the obtained semi-synthetic hydrogels are form-stable, can withstand repeated stress, have a large linear-elastic range, and show strain stiffening behavior typical for biopolymer networks. In addition, it is possible to introduce a positive charge to the core of the cross-linker without affecting the gelation efficiency, or consequently the network connectivity. However, the mechanical properties strongly depend on the charge of the cross-linker. The properties of the presented hydrogels can thus be tuned in a range important for engineering of soft tissues by controlling the cross-linking density and the charge of the cross-linker.

Polymer Crosslinked 3-D Assemblies of Nanoparticles: Mechanically Strong Lightweight Porous Materials

Science.gov (United States)

Leventis, Nicholas

2005-01-01

orders-of-magnitude increase in strength, nevertheless, by varying the polymer we expect to impart other properties such as hydrophobicity, thermal stability and perhaps electrical conductivity. Besides polymers, crosslinkers will include metals and ceramics (e.g., through POSS precursors). Finally, network morphology directs load dissipation, and of approximately 30 different crosslinked oxide aerogels, vanadia, whose structure is fibrous rather than particulate, yields a much stronger (by 4..) material than silica of the same density. It seems imperative to implement control of network morphology, even through templating.

Synthesis and Crosslinking of Polyether-Based Main Chain Benzoxazine Polymers and Their Gas Separation Performance

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Muntazim Munir Khan

2018-02-01

Full Text Available The poly(ethylene glycol-based benzoxazine polymers were synthesized via a polycondensation reaction between Bisphenol-A, paraformaldehyde, and poly(ether diamine/(Jeffamine®. The structures of the polymers were confirmed by proton nuclear magnetic resonance spectroscopy (1H-NMR, indicating the presence of a cyclic benzoxazine ring. The polymer solutions were casted on the glass plate and cross-linked via thermal treatment to produce tough and flexible films without using any external additives. Thermal properties and the crosslinking behaviour of these polymers were studied by thermogravimetric analysis (TGA and differential scanning calorimetry (DSC. Single gas (H2, O2, N2, CO2, and CH4 transport properties of the crosslinked polymeric membranes were measured by the time-lag method. The crosslinked PEG-based polybenzoxazine membranes show improved selectivities for CO2/N2 and CO2/CH4 gas pairs. The good separation selectivities of these PEG-based polybenzoxazine materials suggest their utility as efficient thin film composite membranes for gas and liquid membrane separation technology.

Microporous Organic Polymers Based on Hyper-Crosslinked Coal Tar: Preparation and Application for Gas Adsorption.

Science.gov (United States)

Gao, Hui; Ding, Lei; Bai, Hua; Li, Lei

2017-02-08

Hyper-crosslinked polymers (HCPs) are promising materials for gas capture and storage, but high cost and complicated preparation limit their practical application. In this paper, a new type of HCPs (CTHPs) was synthesized through a one-step mild Friedel-Crafts reaction with low-cost coal tar as the starting material. Chloroform was utilized as both solvent and crosslinker to generate a three-dimensional crosslinked network with abundant micropores. The maximum BET surface area of the prepared CTHPs could reach up to 929 m 2  g -1 . Owing to the high affinity between the heteroatoms on the coal-tar building blocks and the CO 2 molecules, the adsorption capacity of CTHPs towards CO 2 reached up to 14.2 wt % (1.0 bar, 273 K) with a high selectivity (CO 2 /N 2 =32.3). Furthermore, the obtained CTHPs could adsorb 1.27 wt % H 2 at 1.0 bar and 77.3 K, and also showed capacity for the capture of high organic vapors at room temperature. In comparison with other reported porous organic polymers, CTHPs have the advantages of low-cost, easy preparation, and high gas-adsorption performance, making them suitable for mass production and practical use in the future. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid immersion thermal crosslinking of 3D polymer nanopatterns for direct carbonisation with high structural integrity

Science.gov (United States)

Kang, Da-Young; Kim, Cheolho; Park, Gyurim; Moon, Jun Hyuk

2015-12-01

The direct pyrolytic carbonisation of polymer patterns has attracted interest for its use in obtaining carbon materials. In the case of carbonisation of nanopatterned polymers, the polymer flow and subsequent pattern change may occur in order to relieve their high surface energies. Here, we demonstrated that liquid immersion thermal crosslinking of polymer nanopatterns effectively enhanced the thermal resistance and maintained the structure integrity during the heat treatment. We employed the liquid immersion thermal crosslinking for 3D porous SU8 photoresist nanopatterns and successfully converted them to carbon nanopatterns while maintaining their porous features. The thermal crosslinking reaction and carbonisation of SU8 nanopatterns were characterised. The micro-crystallinity of the SU8-derived carbon nanopatterns was also characterised. The liquid immersion heat treatment can be extended to the carbonisation of various polymer or photoresist nanopatterns and also provide a facile way to control the surface energy of polymer nanopatterns for various purposes, for example, to block copolymer or surfactant self-assemblies.

Molecular network considerations in the deformation of glassy polymers

International Nuclear Information System (INIS)

Henkee, C.S.

1985-01-01

Thin films of polystyrene (PS) are crosslinked with electron irradiation and are strained in tension until regions of local plastic deformation, either crazes or plane stress deformation zones (DZ's), have grown. The behavior of the PS glass is consistent with its being a network of molecular strands of total density nu = nu/sub x/ + nu/sub e/, where nu/sub e/ is the entangled strand density, and nu/sub x/ is the density of crosslinked strands. When nu is less than 4 x 10 25 m -3 only crazes are observed. As nu increases from 4 x 10 25 to 8 x 10 -5 m -3 , only shear DZ's are observed. The local extension ratio, lambda, in the crazes and DZ's correlate well with lambda/sub max/, the maximum extension ratio of a strand in a network of density nu computed using the Porod-Kratky model. Crosslinking to still higher crosslink densities, e.g. nu = 14nu/sub e/, results in cracks that propagate in a catastrophic manner at low applied strains. An optimum nu thus exists, one not too high to suppress local shear ductility but high enough to suppress crazes which can act as crack nucleation sites. Comparison of the results in crosslinked PS with those in other linear, but entangled polymer systems implies that chain scission is the major mechanism by which strands in the entanglement network are removed in forming fibril surfaces. Craze suppression by increasing nu is due to the extra energy required to break more main chain bonds to form these surfaces

Reactive polymer fused deposition manufacturing

Science.gov (United States)

Kunc, Vlastimil; Rios, Orlando; Love, Lonnie J.; Duty, Chad E.; Johs, Alexander

2017-05-16

Methods and compositions for additive manufacturing that include reactive or thermosetting polymers, such as urethanes and epoxies. The polymers are melted, partially cross-linked prior to the depositing, deposited to form a component object, solidified, and fully cross-linked. These polymers form networks of chemical bonds that span the deposited layers. Application of a directional electromagnetic field can be applied to aromatic polymers after deposition to align the polymers for improved bonding between the deposited layers.

Rheological analysis of irradiated crosslinkable and scissionable polymers used for medical devices under different radiation conditions

Science.gov (United States)

Satti, A. J.; Ressia, J. A.; Cerrada, M. L.; Andreucetti, N. A.; Vallés, E. M.

2018-03-01

The effects on different synthetic polymers of distinct types of radiation, gamma rays and electron beam, under different atmospheres are followed by changes in their viscoelastic behavior. Taking into account the two main radioinduced reactions, crosslinking and scissioning of polymeric chains, liquid polydimethylsiloxane has been used as example of crosslinkable polymer and semi crystalline polypropylene as example of scissionable polymer. Propylene - 1-hexene copolymers have been also evaluated, and the effects of both reactions were clearly noticed. Accordingly, samples of those aforementioned polymers have been irradiated with 60Co gamma irradiation in air and under vacuum, and also with electron beam, at similar doses. Sinusoidal dynamic oscillation experiments showed a significant increase in branching and crosslinking reactions when specimens are irradiated under vacuum, while scissioning reactions were observed for the different polymers when irradiation takes place under air with either gamma irradiation or electron beam.

Topological structure and mechanics of glassy polymer networks.

Science.gov (United States)

Elder, Robert M; Sirk, Timothy W

2017-11-22

The influence of chain-level network architecture (i.e., topology) on mechanics was explored for unentangled polymer networks using a blend of coarse-grained molecular simulations and graph-theoretic concepts. A simple extension of the Watts-Strogatz model is proposed to control the graph properties of the network such that the corresponding physical properties can be studied with simulations. The architecture of polymer networks assembled with a dynamic curing approach were compared with the extended Watts-Strogatz model, and found to agree surprisingly well. The final cured structures of the dynamically-assembled networks were nearly an intermediate between lattice and random connections due to restrictions imposed by the finite length of the chains. Further, the uni-axial stress response, character of the bond breaking, and non-affine displacements of fully-cured glassy networks were analyzed as a function of the degree of disorder in the network architecture. It is shown that the architecture strongly affects the network stability, flow stress, onset of bond breaking, and ultimate stress while leaving the modulus and yield point nearly unchanged. The results show that internal restrictions imposed by the network architecture alter the chain-level response through changes to the crosslink dynamics in the flow regime and through the degree of coordinated chain failure at the ultimate stress. The properties considered here are shown to be sensitive to even incremental changes to the architecture and, therefore, the overall network architecture, beyond simple defects, is predicted to be a meaningful physical parameter in the mechanics of glassy polymer networks.

Stress-Strain Relation of Tire Rubber Consist of Entangled Polymers, Fillers and Crosslink

Science.gov (United States)

Hagita, Katsumi; Bito, Y.; Minagawa, Y.; Omiya, M.; Morita, H.; Doi, M.; Takano, H.

2009-03-01

We presented a preliminary result of large scale coarse-grained Molecular Dynamics simulation of filled polymer melts with Sulfur-crosslink under an uni-axial deformation by using the Kremer-Grest Model. The size of simulation box under periodic boundary conditions (PBC) is set to about 66nm to consider length of entangled polymer chains, size and structure of fillers, and non-uniform distribution of crosslink. We put 640 polymer chains of 1024 particles and 32 fillers into the PBC box. Each filler consists of 1280 particles of the C1280 fullerene structure. A repulsive force from the center of the filler is applied to the particles. Here, the particles of the fillers are chosen to be the same as the particles of the polymers and the diameter of the filler is about 15nm. The distribution of the fillers used in this simulation is provided by the result of 2d pattern RMC analysis for 2D-USAXS experiments at SPring-8. Sulfur crosslink are randomly distributed in the system. It is found that stress-strain curves estimated by applying a certain uni-axial deformation to the system in simulations are in good agreement with those in experiments. It is successful to show difference on the S-S curve between existence / absence of fillers and qualitative dependence of attractive force between polymer and filler.

Radiation cross-linking of PTC conductive polymers

International Nuclear Information System (INIS)

Doljack, F.A.; Jacobs, S.M.; Taylor, J.M.; McTavish, M.S.

1982-01-01

An electrical device comprising a PTC conductive polymer is irradiated so that it is very highly cross-linked. A dosage of at least 50 Mrads, preferably at least 80 Mrads, especially at least 120 Mrads is used except that where the device includes planar electrodes which are present during irradiation the minimum dose is 120 Mrads. In this way, for example, it is possible to make a circuit protection device which will continue to provide effective protection even after repeated exposure to a voltage of 200 volts. A PTC protection device may be produced by moulding carbon loaded polymer round three electrodes the centre one of which is then removed to leave an aperture between the other two electrodes. (author)

Recycling and processing of several typical crosslinked polymer scraps with enhanced mechanical properties based on solid-state mechanochemical milling

Energy Technology Data Exchange (ETDEWEB)

Lu, Canhui; Zhang, Xinxing; Zhang, Wei [State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute, Sichuan University, Chengdu 610065 (China)

2015-05-22

The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. The results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps.

Recycling and processing of several typical crosslinked polymer scraps with enhanced mechanical properties based on solid-state mechanochemical milling

Science.gov (United States)

Lu, Canhui; Zhang, Xinxing; Zhang, Wei

2015-05-01

The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. The results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps.

Recycling and processing of several typical crosslinked polymer scraps with enhanced mechanical properties based on solid-state mechanochemical milling

International Nuclear Information System (INIS)

Lu, Canhui; Zhang, Xinxing; Zhang, Wei

2015-01-01

The partially devulcanization or de-crosslinking of ground tire rubber (GTR), post-vulcanized fluororubber scraps and crosslinked polyethylene from cable scraps through high-shear mechanochemical milling (HSMM) was conducted by a modified solid-state mechanochemical reactor. The results indicated that the HSMM treated crosslinked polymer scraps can be reprocessed as virgin rubbers or thermoplastics to produce materials with high performance. The foamed composites of low density polyethylene/GTR and the blend of post-vulcanized flurorubber (FKM) with polyacrylate rubber (ACM) with better processability and mechanical properties were obtained. The morphology observation showed that the dispersion and compatibility between de-crosslinked polymer scraps and matrix were enhanced. The results demonstrated that HSMM is a feasible alternative technology for recycling post-vulcanized or crosslinked polymer scraps

Efficient protein-repelling thin films regulated by chain mobility of low-Tg polymers with increased stability via crosslinking

Science.gov (United States)

Zhang, Jinghui; Huang, Zhiwei; Liu, Dan

2017-12-01

Polymer thin films are generally employed as coatings on implants to prevent protein adsorption. Polymer chain mobility and surface softness have been found to contribute to the protein resistance, but also bring film instability in a liquid protein medium. We investigated the protein resistance ability of three low-Tg polymers, including hydrophobic polymers polyisoprene (PI), poly(n-butyl methacrylate) (PnBMA) and hydrophilic polyethylene oxide (PEO), by overcoming the instability issue with crosslinking. We found that the Tgs of PI and PEO can be increased to around 0 °C after crosslinking. The remained strong chain mobility of both films can still resist protein adsorption regardless the hydrophobicity, yet greatly increases the film stability under an aqueous circumstance. The PnBMA film increased its Tg to around room temperature after crosslinking, which deteriorated the protein-resistance ability having the surface covered by BSA molecules. Our results support that the chain mobility of a polymer film plays an important role in resisting protein adsorption due to the increased entropy associated with more mobile polymer chains. By tune the degree of crosslinking, the stability of polymer in aqueous environment can be increased while the protein resistant ability can be remained. Our results provide a new strategy to design polymer materials for effective antifouling.

Interpenetrating polymer networks from acetylene terminated materials

Science.gov (United States)

Connell, J. W.; Hergenrother, P. M.

1989-01-01

As part of a program to develop high temperature/high performance structural resins for aerospace applications, the chemistry and properties of a novel class of interpenetrating polymer networks (IPNs) were investigated. These IPNs consist of a simple diacetylenic compound (aspartimide) blended with an acetylene terminated arylene ether oligomer. Various compositional blends were prepared and thermally cured to evaluate the effect of crosslink density on resin properties. The cured IPNs exhibited glass transition temperatures ranging from 197 to 254 C depending upon the composition and cure temperature. The solvent resistance, fracture toughness and coefficient of thermal expansion of the cured blends were related to the crosslink density. Isothermal aging of neat resin moldings, adhesive and composite specimens showed a postcure effect which resulted in improved elevated temperature properties. The chemistry, physical and mechanical properties of these materials will be discussed.

Radiation synthesis and characterization of network structure of natural/synthetic double-network superabsorbent polymers

International Nuclear Information System (INIS)

Sen, M.; Hayrabolulu, H.

2011-01-01

Complete text of publication follows. Superabsorbent polymers (SAPs) are moderately cross linked, 3-D, hydrophilic network polymers that can absorb and conserve considerable amounts of aqueous fluids even under certain heat or pressure. Because of the unique properties superior to conventional absorbents, SAPs have found potential application in many fields such as hygienic products, disposable diapers, horticulture, gel actuators, drug-delivery systems, as well as water-blocking tapes coal dewatering, water managing materials for the renewal of arid and desert environment, etc. In recent years, naturally available resources, such as polysaccharides have drawn considerable attention for the preparation of SAPs. Since the mechanical properties of polysaccharide based natural polymers are low, researchers have mostly focused on natural/synthetic polymer/monomer mixtures to obtain novel SAPs. The aim of this study is to synthesize and characterization of network structure of novel double-network (DN) hydrogels as a SAP. Hydrogels with high mechanical strength have been prepared by radiation induced polymerization and crosslink of acrylic acid sodium salt in the presence of natural polymer locust bean gum. Liquid retention capacities and absorbency under load (AUL) analysis of synthesized SAPs was performed at different temperatures in water and synthetic urine solution, in order to determine their SAP character. For the characterization of network structure of the semi-IPN hydrogels, the average molecular weight between cross links (M c ) were evaluated by using uniaxial compression and oscillatory dynamical mechanical analyses and the advantage and disadvantage of these two technique for the characterization of network structures were compared.

Dissolution of covalent adaptable network polymers in organic solvent

Science.gov (United States)

Yu, Kai; Yang, Hua; Dao, Binh H.; Shi, Qian; Yakacki, Christopher M.

2017-12-01

It was recently reported that thermosetting polymers can be fully dissolved in a proper organic solvent utilizing a bond-exchange reaction (BER), where small molecules diffuse into the polymer, break the long polymer chains into short segments, and eventually dissolve the network when sufficient solvent is provided. The solvent-assisted dissolution approach was applied to fully recycle thermosets and their fiber composites. This paper presents the first multi-scale modeling framework to predict the dissolution kinetics and mechanics of thermosets in organic solvent. The model connects the micro-scale network dynamics with macro-scale material properties: in the micro-scale, a model is developed based on the kinetics of BERs to describe the cleavage rate of polymer chains and evolution of chain segment length during the dissolution. The micro-scale model is then fed into a continuum-level model with considerations of the transportation of solvent molecules and chain segments in the system. The model shows good prediction on conversion rate of functional groups, degradation of network mechanical properties, and dissolution rate of thermosets during the dissolution. It identifies the underlying kinetic factors governing the dissolution process, and reveals the influence of different material and processing variables on the dissolution process, such as time, temperature, catalyst concentration, and chain length between cross-links.

Crosslinked polyurethanes based on hyperbranched polymers

Directory of Open Access Journals (Sweden)

Vuković Jasna

2008-01-01

Full Text Available In this paper, two samples of polyurethane (PU crosslinked with hydroxy -functonal hyperbranched aliphatic polyester of the second pseudo generation were investigated. For the synthesis of these crosslinked PUs two different macrodiols were used: poly(tetramethyleneoxide (PTMO for PUPTMO and ethylene oxide-poly(dimethylsiloxane-ethylene oxide (PDMS-EO for PUPDMS-EO sample. Synthesized samples behave as elastomers and have yellow color. Obtained results show that swelling degree of the sample PUPDMS-EO in N-methyl-2-pyrrolidinon (NMP determined at room temperature is higher than for the sample PUPTMO. It has been also observed that thermal properties of these polyurethane networks can be changed by incorporation of siloxane sequences in their structure.

Azide-based cross-linking of polymers of intrinsic microporosity (PIMs) for condensable gas separation

KAUST Repository

Du, Naiying

2011-03-11

Cross-linked polymers of intrinsic microporosity (PIM)s for gas separation membranes, were prepared by a nitrene reaction from a representative PIM in the presence of two different diazide cross-linkers. The reaction temperature was optimized using TGA. The homogenous membranes were cast from THF solutions of different ratios of PIM to azides. The resulting cross-linked structures of the PIMs membranes were formed at 175 °C after 7.5 h and confirmed by TGA, XPS, FT-IR spectroscopy and gel content analysis. These resulting cross-linked polymeric membranes showed excellent gas separation performance and can be used for O 2/N 2 and CO 2/N 2 gas pairs, as well as for condensable gases, such as CO 2/CH 4, propylene/propane separation. Most importantly, and differently from typical gas separation membranes derived from glassy polymers, the crosslinked PIMs showed no obvious CO 2 plasticization up to 20 atm pressure of pure CO 2 and CO 2/CH 4 mixtures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Azide-based cross-linking of polymers of intrinsic microporosity (PIMs) for condensable gas separation

KAUST Repository

Du, Naiying; Dal-Cin, Mauro M D; Pinnau, Ingo; Nicalek, Andrzej; Robertson, Gilles P.; Guiver, Michael D.

2011-01-01

Cross-linked polymers of intrinsic microporosity (PIM)s for gas separation membranes, were prepared by a nitrene reaction from a representative PIM in the presence of two different diazide cross-linkers. The reaction temperature was optimized using TGA. The homogenous membranes were cast from THF solutions of different ratios of PIM to azides. The resulting cross-linked structures of the PIMs membranes were formed at 175 °C after 7.5 h and confirmed by TGA, XPS, FT-IR spectroscopy and gel content analysis. These resulting cross-linked polymeric membranes showed excellent gas separation performance and can be used for O 2/N 2 and CO 2/N 2 gas pairs, as well as for condensable gases, such as CO 2/CH 4, propylene/propane separation. Most importantly, and differently from typical gas separation membranes derived from glassy polymers, the crosslinked PIMs showed no obvious CO 2 plasticization up to 20 atm pressure of pure CO 2 and CO 2/CH 4 mixtures. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Deformation and concentration fluctuations under stretching in a polymer network with free chains. The ''butterfly'' effect

International Nuclear Information System (INIS)

Ramzi, A.

1994-06-01

Small Angle Neutron Scattering gives access to concentration fluctuations of mobile labeled polymer chains embedded in a polymer network. At rest they appear progressively larger than for random mixing, with increasing ratio. Under uniaxial stretching, they decrease towards ideal mixing along the direction perpendicular to stretching, and can grow strongly along the parallel one, including the zero scattering vector q limit. This gives rise to intensity contours with double-winged patterns, in the shape of the figure '8', or of 'butterfly'. Random crosslinking and end-linking of monodisperse chains have both been studied. The strength of the 'butterfly' effect increases with the molecular weight of the free chains, the crosslinking ratio, the network heterogeneity, and the elongation ratio. Eventually, the signal collapses on an 'asymptotic' function I(q), of increasing correlation length with the elongation ratio. Deformation appears heterogeneous, maximal for soft areas, where the mobile chains localize preferentially. This could be due to spontaneous fluctuations, or linked to frozen fluctuations of the crosslink density. However, disagreement with the corresponding theoretical expressions makes it necessary to account for the spatial correlations of crosslink density, and their progressive unscreening as displayed by the asymptotic behavior. Networks containing pending labeled chains and free labeled stars lead to more precise understanding of the diffusion of free species and the heterogeneity of the deformation. It seems that the latter occurs even without diffusion for heterogeneous enough networks. In extreme cases (of the crosslinking parameters), the spatial correlations display on apparent fractal behavior, of dimensions 2 to 2.5, which is discussed here in terms of random clusters. 200 refs., 95 figs., 21 tabs., 10 appends

Conductivity and properties of polysiloxane-polyether cluster-LiTFSI networks as hybrid polymer electrolytes

Science.gov (United States)

Boaretto, Nicola; Joost, Christine; Seyfried, Mona; Vezzù, Keti; Di Noto, Vito

2016-09-01

This report describes the synthesis and the properties of a series of polymer electrolytes, composed of a hybrid inorganic-organic matrix doped with LiTFSI. The matrix is based on ring-like oligo-siloxane clusters, bearing pendant, partially cross-linked, polyether chains. The dependency of the thermo-mechanic and of the transport properties on several structural parameters, such as polyether chains' length, cross-linkers' concentration, and salt concentration is studied. Altogether, the materials show good thermo-mechanical and electrochemical stabilities, with conductivities reaching, at best, 8·10-5 S cm-1 at 30 °C. In conclusion, the cell performances of one representative sample are shown. The scope of this report is to analyze the correlations between structure and properties in networked and hybrid polymer electrolytes. This could help the design of optimized polymer electrolytes for application in lithium metal batteries.

Ionic liquids in a poly ethylene oxide cross-linked gel polymer as an electrolyte for electrical double layer capacitor

Science.gov (United States)

Chaudoy, V.; Tran Van, F.; Deschamps, M.; Ghamouss, F.

2017-02-01

In the present work, we developed a gel polymer electrolyte via the incorporation of a room temperature ionic liquid into a cross-linked polymer matrix. The cross-linked gel electrolyte was prepared using a free radical polymerization of methacrylate and dimethacrylate oligomers dissolved in 1-propyl-1-methylpyrrolidinium bis(fluorosulfonyl)imide. Combining the advantages of the ionic liquids and of conventional polymers, the cross-linked gel polymer electrolyte was used both as a separator and as an electrolyte for a leakage-free and non-flammable EDLC supercapacitor. The quasi-all solid-state supercapacitors showed rather good capacitance, power and energy densities by comparison to a liquid electrolyte-based EDLC.

3.3. Sorption activity of cross-linked polymers of ethynyl-piperidol

International Nuclear Information System (INIS)

Khalikov, D.Kh.

2012-01-01

The sorption activity of cross-linked polymers of ethynyl-piperidol was studied. The bilirubin sorption was studied as well. The kinetic of bilirubin sorption and human serum albumin at their joint presence in hydrogel solutions was defined. Bilirubin sorption and change of albumin composition was considered. The sorption of middle molecular peptides was considered as well. The sorption of endogenous toxin by means of ethynyl-piperidol polymers was done.

Anisotropically Swelling Gels Attained through Axis-Dependent Crosslinking of MOF Crystals.

Science.gov (United States)

Ishiwata, Takumi; Kokado, Kenta; Sada, Kazuki

2017-03-01

Anisotropically deforming objects have attracted considerable interest for use in molecular machines and artificial muscles. Herein, we focus on a new approach based on the crystal crosslinking of organic ligands in a pillared-layer metal-organic framework (PLMOF). The approach involves the transformation from crosslinked PLMOF to polymer gels through hydrolysis of the coordination bonds between the organic ligands and metal ions, giving a network polymer that exhibits anisotropic swelling. The anisotropic monomer arrangement in the PLMOF underwent axis-dependent crosslinking to yield anisotropically swelling gels. Therefore, the crystal crosslinking of MOFs should be a useful method for creating actuators with designable deformation properties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photo-crosslinkable polymers for fabrication of photonic multilayer sensors

Science.gov (United States)

Chiappelli, Maria; Hayward, Ryan C.

2013-03-01

We have used photo-crosslinkable polymers to fabricate photonic multilayer sensors. Benzophenone is utilized as a covalently incorporated pendent photo-crosslinker, providing a convenient means of fabricating multilayer films by sequential spin-coating and crosslinking processes. Colorimetric temperature sensors were designed from thermally-responsive, low-refractive index poly(N-isopropylacrylamide) (PNIPAM) and high-refractive index poly(para-methyl styrene) (P pMS). Copolymer chemistries and layer thicknesses were selected to provide robust multilayer sensors which show color changes across nearly the full visible spectrum due to changes in temperature of the hydrated film stack. We have characterized the uniformity and interfacial broadening within the multilayers, the kinetics of swelling and de-swelling, and the reversibility over multiple hydration/dehydration cycles. We also describe how the approach can be extended to alternative sensor designs through the ability to tailor each layer independently, as well as to additional stimuli by selecting alternative copolymer chemistries.

Dynamic behavior of dual cross-linked nanoparticle networks under oscillatory shear

International Nuclear Information System (INIS)

Iyer, Balaji V S; Yashin, Victor V; Balazs, Anna C

2014-01-01

Via computer simulations, we investigate the linear and nonlinear viscoelastic response of polymer grafted nanoparticle networks subject to oscillatory shear at different amplitudes and frequencies. The individual nanoparticles are composed of a rigid spherical core and a corona of grafted polymers that encompass reactive end groups. With the overlap of the coronas on adjacent particles, the reactive end groups form permanent or labile bonds, and thus form a ‘dual cross-linked’ network. The existing labile bonds between particles can break and reform depending on the bond rupture rate, extent of deformation and the frequency of oscillation. We study how the viscoelastic behavior of the material depends on the energy of the labile bonds and identify the network characteristics that give rise to the observed viscoelastic response. We observe that with an increase in labile bond energy, the storage modulus increases while the loss modulus shows a more complex response depending on the labile bond energy. Specifically, in the case of the samples with the weaker labile bonds, the loss modulus increases monotonically, while for the samples with the stronger labile bonds, the loss modulus exhibits a minimum with an increase in frequency. We show that an increase in the storage modulus corresponds to an enhancement in the average number of bonds in the samples and the characteristics of the loss modulus depend on both the bond kinetics and the mobility of the particles in the network. Furthermore, we determine that the effective contribution of the bonds to the storage modulus decreases with increase in strain amplitude. In particular, while bond formation at small amplitude drives an increase in storage modulus, at large amplitudes it promotes clustering and formation of voids leading to strain softening. Our simulations provide a mesoscopic picture of how the nature of labile bonds affects the performance of cross-linked polymer-grafted nanoparticle networks. (paper)

Charged Triazole Cross-Linkers for Hyaluronan-Based Hybrid Hydrogels

Directory of Open Access Journals (Sweden)

Maike Martini

2016-09-01

Full Text Available Polyelectrolyte hydrogels play an important role in tissue engineering and can be produced from natural polymers, such as the glycosaminoglycan hyaluronan. In order to control charge density and mechanical properties of hyaluronan-based hydrogels, we developed cross-linkers with a neutral or positively charged triazole core with different lengths of spacer arms and two terminal maleimide groups. These cross-linkers react with thiolated hyaluronan in a fast, stoichiometric thio-Michael addition. Introducing a positive charge on the core of the cross-linker enabled us to compare hydrogels with the same interconnectivity, but a different charge density. Positively charged cross-linkers form stiffer hydrogels relatively independent of the size of the cross-linker, whereas neutral cross-linkers only form stable hydrogels at small spacer lengths. These novel cross-linkers provide a platform to tune the hydrogel network charge and thus the mechanical properties of the network. In addition, they might offer a wide range of applications especially in bioprinting for precise design of hydrogels.

High Performance Polymer Field-Effect Transistors Based on Thermally Crosslinked Poly(3-hexylthiophene)

International Nuclear Information System (INIS)

Jiang Chun-Xia; Yang Xiao-Yan; Zhao Kai; Wu Xiao-Ming; Yang Li-Ying; Cheng Xiao-Man; Yin Shou-Gen; Wei Jun

2011-01-01

The performance of polymer field-effect transistors is improved by thermal crosslinking ofpoly(3-hexylthiophene), using ditert butyl peroxide as the crosslinker. The device performance depends on the crosslinker concentration significantly. We obtain an optimal on/off ratio of 10 5 and the saturate field-effect mobility of 0.34cm 2 V −1 s −1 , by using a suitable ratios of ditert butyl peroxide, 0.5 wt% ofpoly(3-hexylthiophene). The microstructure images show that the crosslinked poly(3-hexylthiophene) active layers simultaneously possess appropriate crystallinity and smooth morphology. Moreover, crosslinking of poly(3-hexylthiophene) prevents the transistors from large threshold voltage shifts under ambient bias-stressing, showing an advantage in encouraging device environmental and operating stability. (cross-disciplinary physics and related areas of science and technology)

Investigation of Cross-Linked and Additive Containing Polymer Materials for Membranes with Improved Performance in Pervaporation and Gas Separation

Directory of Open Access Journals (Sweden)

Karl Kleinermanns

2012-10-01

Full Text Available Pervaporation and gas separation performances of polymer membranes can be improved by crosslinking or addition of metal-organic frameworks (MOFs. Crosslinked copolyimide membranes show higher plasticization resistance and no significant loss in selectivity compared to non-crosslinked membranes when exposed to mixtures of CO2/CH4 or toluene/cyclohexane. Covalently crosslinked membranes reveal better separation performances than ionically crosslinked systems. Covalent interlacing with 3-hydroxypropyldimethylmaleimide as photocrosslinker can be investigated in situ in solution as well as in films, using transient UV/Vis and FTIR spectroscopy. The photocrosslinking yield can be determined from the FTIR-spectra. It is restricted by the stiffness of the copolyimide backbone, which inhibits the photoreaction due to spatial separation of the crosslinker side chains. Mixed-matrix membranes (MMMs with MOFs as additives (fillers have increased permeabilities and often also selectivities compared to the pure polymer. Incorporation of MOFs into polysulfone and Matrimid® polymers for MMMs gives defect-free membranes with performances similar to the best polymer membranes for gas mixtures, such as O2/N2 H2/CH4, CO2/CH4, H2/CO2, CH4/N2 and CO2/N2 (preferentially permeating gas is named first. The MOF porosity, its particle size and content in the MMM are factors to influence the permeability and the separation performance of the membranes.

Investigation of cross-linked and additive containing polymer materials for membranes with improved performance in pervaporation and gas separation.

Science.gov (United States)

Hunger, Katharina; Schmeling, Nadine; Jeazet, Harold B Tanh; Janiak, Christoph; Staudt, Claudia; Kleinermanns, Karl

2012-10-22

Pervaporation and gas separation performances of polymer membranes can be improved by crosslinking or addition of metal-organic frameworks (MOFs). Crosslinked copolyimide membranes show higher plasticization resistance and no significant loss in selectivity compared to non-crosslinked membranes when exposed to mixtures of CO2/CH4 or toluene/cyclohexane. Covalently crosslinked membranes reveal better separation performances than ionically crosslinked systems. Covalent interlacing with 3-hydroxypropyldimethylmaleimide as photocrosslinker can be investigated in situ in solution as well as in films, using transient UV/Vis and FTIR spectroscopy. The photocrosslinking yield can be determined from the FTIR-spectra. It is restricted by the stiffness of the copolyimide backbone, which inhibits the photoreaction due to spatial separation of the crosslinker side chains. Mixed-matrix membranes (MMMs) with MOFs as additives (fillers) have increased permeabilities and often also selectivities compared to the pure polymer. Incorporation of MOFs into polysulfone and Matrimid® polymers for MMMs gives defect-free membranes with performances similar to the best polymer membranes for gas mixtures, such as O2/N2 H2/CH4, CO2/CH4, H2/CO2, CH4/N2 and CO2/N2 (preferentially permeating gas is named first). The MOF porosity, its particle size and content in the MMM are factors to influence the permeability and the separation performance of the membranes.

Core Cross-linked Star Polymers for Temperature/pH Controlled Delivery of 5-Fluorouracil

Directory of Open Access Journals (Sweden)

Elizabeth Sánchez-Bustos

2016-01-01

Full Text Available RAFT polymerization with cross-linking was used to prepare core cross-linked star polymers bearing temperature sensitive arms. The arms consisted of a diblock copolymer containing N-isopropylacrylamide (NIPAAm and 4-methacryloyloxy benzoic acid (4MBA in the temperature sensitive block and poly(hexyl acrylate forming the second hydrophobic block, while ethyleneglycol dimethacrylate was used to form the core. The acid comonomer provides pH sensitivity to the arms and also increases the transition temperature of polyNIPAAm to values in the range of 40 to 46°C. Light scattering and atomic force microscopy studies suggest that loose core star polymers were obtained. The star polymers were loaded with 5-fluorouracil (5-FU, an anticancer agent, in values of up to 30 w/w%. In vitro release experiments were performed at different temperatures and pH values, as well as with heating and cooling temperature cycles. Faster drug release was obtained at 42°C or pH 6, compared to normal physiological conditions (37°C, pH 7.4. The drug carriers prepared acted as nanopumps changing the release kinetics of 5-FU when temperatures cycles were applied, in contrast with release rates at a constant temperature. The prepared core cross-linked star polymers represent advanced drug delivery vehicles optimized for 5-FU with potential application in cancer treatment.

Copper-catalyzed azide alkyne cycloaddition polymer networks

Science.gov (United States)

Alzahrani, Abeer Ahmed

-CuAAC reaction and a chain-growth acrylate homopolymerization were demonstrated and used to form branched polymer structures. A bulk, organic soluble initiation system consisting of a Cu(II) salt and a primary amine was also examined in both model reactions and in bulk polymerizations. The system was shown to be highly efficient, leading to nearly complete CuAAC polymerization at ambient temperature. Increasing the ratio of amine to copper from 1 to 4 increases the CuAAC reaction rate significantly from 4 mM/min for 1:1 ratio of Cu(II):hexyalmine to 14mM/min for 1:4 ratio. The concentration dependence of the amine on the reaction rate enables the polymerization rate to be controlled simply by manipulating the hexylamine concentration. Sequential thiol--acrylate and photo-CuAAC click reactions were utilized to form two-stage reactive polymer networks capable of generating wrinkles in a facile manner. The click thiol-Michael addition reaction was utilized to form a cross-linked polymer with residual, reactive alkyne sites that remained tethered throughout the network. The latent, unreacted alkyne sites are subsequently reacted with diazide monomers via a photoinduced Cu(I)-catalyzed alkyne-azide cycloaddition (CuAAC) reaction to increase the cross-link density. Increased cross-linking raised the modulus and glass transition temperature from 1.6 MPa and 2 °C after the thiol-acrylate reaction to 4.4 MPa and 22 °C after the CuAAC reaction, respectively. The double click reaction approach led to micro-wrinkles with well-controlled wavelength and amplitude of 8.50 +/- 1.6 and 1.4 μm, respectively, for a polymer with a 1280 μm total film thickness. Additionally, this approach further enables spatial selectivity of wrinkle formation by photo-patterning. The CuAAC-based polymerization was also used to design smart, responsive porous materials from well-defined CuAAC networks, which possesses a high glass transition temperature (Tg= 115°C) due to the formation of the triazole linkages

New Aptes Cross-linked Polymers from Poly(ethylene oxide)s and Cyanuric Chloride for Lithium Batteries

Science.gov (United States)

Tigelaar, Dean M.; Meador, Mary Ann B.; Kinder, James D.; Bennett, William R.

2005-01-01

A new series of polymer electrolytes for use as membranes for lithium batteries are described. Electrolytes were made by polymerization between cyanuric chloride and diamino-terminated poly(ethylene oxide)s, followed by cross-linking via a sol-gel process. Thermal analysis and lithium conductivity of freestanding polymer films were studied. The effects of several variables on conductivity were investigated, such as length of backbone PEO chain, length of branching PEO chain, extent of branching, extent of cross-linking, salt content, and salt counterion. Polymer films with the highest percentage of PEO were found to be the most conductive, with a maximum lithium conductivity of 3.9 x 10(exp -5) S/cm at 25 C. Addition of plasticizer to the dry polymers increased conductivity by an order of magnitude.

Effect of cross-linkable polymer on the morphology and properties of transparent multi-walled carbon nanotube conductive films

International Nuclear Information System (INIS)

Huang, Yuan-Li; Tien, Hsi-Wen; Ma, Chen-Chi M.; Teng, Chih-Chun; Yu, Yi-Hsiuan; Yang, Shin-Yi; Wei, Ming-Hsiung; Wu, Sheng-Yen

2011-01-01

In this study, we fabricated optically transparent and electrically conductive multi-walled carbon nanotube (MWCNT) thin films using a spray-coating technique. The transparency and the electrical resistance of thin film are dependent on the nanotube content deposited on the polyethylene terephthalate (PET) substrate. Poly(acrylic acid) (PAA) and poly(N-vinyl pyrrolidone) (PVP) were used as adhesion promoters to improve MWCNT coating more significantly. The cross-linked polymer resulted in a superior bond between the MWCNTs and the substrates. The surface electrical resistance was significantly lower than the original sheet after nitric acid (HNO 3 ) treatment because of the removed surfactant and the increased interconnecting networks of MWCNT bundles, thus improving the electrical and optical properties of the films. Stronger interaction between the MWCNTs and the substrates resulted in lower decomposition of the polymer chain and less amounts of MWCNTs separated into the HNO 3 solution. The lower sheet electrical resistance of PVP/PAA-g-MWCNT conductive films on the PET substrate was because of a more complete conductive path with the cross-linked polymer than that without. Such an improved sheet of electrical resistance varied from 8.83 x 10 4 Ω/□ to 2.65 x 10 3 Ω/□ with 5.0 wt.% PVP/PAA-g-MWCNT sprayed on the PET after acid treatment.

Effect of cross-linkable polymer on the morphology and properties of transparent multi-walled carbon nanotube conductive films

Science.gov (United States)

Huang, Yuan-Li; Tien, Hsi-Wen; Ma, Chen-Chi M.; Teng, Chih-Chun; Yu, Yi-Hsiuan; Yang, Shin-Yi; Wei, Ming-Hsiung; Wu, Sheng-Yen

2011-10-01

In this study, we fabricated optically transparent and electrically conductive multi-walled carbon nanotube (MWCNT) thin films using a spray-coating technique. The transparency and the electrical resistance of thin film are dependent on the nanotube content deposited on the polyethylene terephthalate (PET) substrate. Poly(acrylic acid) (PAA) and poly(N-vinyl pyrrolidone) (PVP) were used as adhesion promoters to improve MWCNT coating more significantly. The cross-linked polymer resulted in a superior bond between the MWCNTs and the substrates. The surface electrical resistance was significantly lower than the original sheet after nitric acid (HNO 3) treatment because of the removed surfactant and the increased interconnecting networks of MWCNT bundles, thus improving the electrical and optical properties of the films. Stronger interaction between the MWCNTs and the substrates resulted in lower decomposition of the polymer chain and less amounts of MWCNTs separated into the HNO 3 solution. The lower sheet electrical resistance of PVP/PAA-g-MWCNT conductive films on the PET substrate was because of a more complete conductive path with the cross-linked polymer than that without. Such an improved sheet of electrical resistance varied from 8.83 × 10 4 Ω/□ to 2.65 × 10 3 Ω/□ with 5.0 wt.% PVP/PAA-g-MWCNT sprayed on the PET after acid treatment.

Transient response of nonlinear polymer networks: A kinetic theory

Science.gov (United States)

Vernerey, Franck J.

2018-06-01

Dynamic networks are found in a majority of natural materials, but also in engineering materials, such as entangled polymers and physically cross-linked gels. Owing to their transient bond dynamics, these networks display a rich class of behaviors, from elasticity, rheology, self-healing, or growth. Although classical theories in rheology and mechanics have enabled us to characterize these materials, there is still a gap in our understanding on how individuals (i.e., the mechanics of each building blocks and its connection with others) affect the emerging response of the network. In this work, we introduce an alternative way to think about these networks from a statistical point of view. More specifically, a network is seen as a collection of individual polymer chains connected by weak bonds that can associate and dissociate over time. From the knowledge of these individual chains (elasticity, transient attachment, and detachment events), we construct a statistical description of the population and derive an evolution equation of their distribution based on applied deformation and their local interactions. We specifically concentrate on nonlinear elastic response that follows from the strain stiffening response of individual chains of finite size. Upon appropriate averaging operations and using a mean field approximation, we show that the distribution can be replaced by a so-called chain distribution tensor that is used to determine important macroscopic measures such as stress, energy storage and dissipation in the network. Prediction of the kinetic theory are then explored against known experimental measurement of polymer responses under uniaxial loading. It is found that even under the simplest assumptions of force-independent chain kinetics, the model is able to reproduce complex time-dependent behaviors of rubber and self-healing supramolecular polymers.

Tough Self-Healing Elastomers by Molecular Enforced Integration of Covalent and Reversible Networks.

Science.gov (United States)

Wu, Jinrong; Cai, Li-Heng; Weitz, David A

2017-10-01

Self-healing polymers crosslinked by solely reversible bonds are intrinsically weaker than common covalently crosslinked networks. Introducing covalent crosslinks into a reversible network would improve mechanical strength. It is challenging, however, to apply this concept to "dry" elastomers, largely because reversible crosslinks such as hydrogen bonds are often polar motifs, whereas covalent crosslinks are nonpolar motifs. These two types of bonds are intrinsically immiscible without cosolvents. Here, we design and fabricate a hybrid polymer network by crosslinking randomly branched polymers carrying motifs that can form both reversible hydrogen bonds and permanent covalent crosslinks. The randomly branched polymer links such two types of bonds and forces them to mix on the molecular level without cosolvents. This enables a hybrid "dry" elastomer that is very tough with fracture energy 13500 Jm -2 comparable to that of natural rubber. Moreover, the elastomer can self-heal at room temperature with a recovered tensile strength 4 MPa, which is 30% of its original value, yet comparable to the pristine strength of existing self-healing polymers. The concept of forcing covalent and reversible bonds to mix at molecular scale to create a homogenous network is quite general and should enable development of tough, self-healing polymers of practical usage. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Glass transition temperatures of microphase separated semi-interpenetrating polymer networks of polystyrene-inter-poly(cross)-2-ethylhexyl-methacrylate

NARCIS (Netherlands)

de Graaf, L.A.; de Graaf, Leontine A.; Möller, Martin; Moller, M.

1995-01-01

The glass transition temperature of semi-interpenetrating polymer networks (semi-IPNs) of atactic polystyrene (PS) in crosslinked methacrylates was studied by systematic variation of the morphology, that is domain size, continuity and concentration in the domains. Semi-IPNs were prepared from

Crosslinkable fumed silica-based nanocomposite electrolytes for rechargeable lithium batteries

Energy Technology Data Exchange (ETDEWEB)

Li, Yangxing; Yerian, Jeffrey A.; Khan, Saad A.; Fedkiw, Peter S. [Department of Chemical & amp; Biomolecular Engineering, North Carolina State University, Raleigh, NC 27695-7905 (United States)

2006-10-27

Electrochemical and rheological properties are reported of composite polymer electrolytes (CPEs) consisting of dual-functionalized fumed silica with methacrylate and octyl groups+low-molecular weight poly(ethylene glycol) dimethyl ether (PEGdm)+lithium bis(trifluoromethanesulfonyl)imide (LiTFSI, lithium imide)+butyl methacrylate (BMA). The role of butyl methacrylate, which aids in formation of a crosslinked network by tethering adjacent fumed silica particles, on rheology and electrochemistry is examined together with the effects of fumed silica surface group, fumed silica weight percent, salt concentration, and solvent molecular weight. Chemical crosslinking of the fumed silica with 20% BMA shows a substantial increase in the elastic modulus of the system and a transition from a liquid-like/flocculated state to an elastic network. In contrast, no change in lithium transference number and only a modest decrease (factor of 2) on conductivity of the CPE are observed, indicating that a crosslinked silica network has minimal effect on the mechanism of ionic transport. These trends suggest that the chemical crosslinks occur on a microscopic scale, as opposed to a molecular scale, between adjacent silica particles and therefore do not impede the segmental mobility of the PEGdm. The relative proportion of the methacrylate and octyl groups on the silica surface displays a nominal effect on both rheology and conductivity following crosslinking although the pre-cure rheology is a function of the surface groups. Chemical crosslinked nanocomposite polymer electrolytes offer significant higher elastic modulus and yield stress than the physical nanocomposite counterpart with a small/negligible penalty of transport properties. The crosslinked CPEs exhibit good interfacial stability with lithium metal at open circuit, however, they perform poorly in cycling of lithium-lithium cells. (author)

Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

KAUST Repository

Vidal, Fernando

2016-07-07

The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

Robust Crosslinked Stereocomplexes and C60 Inclusion Complexes of Vinyl-Functionalized Stereoregular Polymers Derived from Chemo/Stereoselective Coordination Polymerization

KAUST Repository

Vidal, Fernando; Falivene, Laura; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene Y.-X.

2016-01-01

The successful synthesis of highly syndiotactic polar vinyl polymers bearing the reactive pendant vinyl group on each repeat unit, which is enabled by perfectly chemoselective and highly syndiospecific coordination polymerization of divinyl polar monomers developed through this work, has allowed the construction of robust crosslinked supramolecular stereocomplexes and C60 inclusion complexes. The metal-mediated coordination polymerization of three representative polar divinyl monomers, including vinyl methacrylate (VMA), allyl methacrylate (AMA), and N,N-diallyl acrylamide (DAA) by Cs-ligated zirconocenium ester enolate catalysts under ambient conditions exhibits complete chemoselectivity and high stereoselectivity, thus producing the corresponding vinyl-functionalized polymers with high (92% rr) to quantitative (>99% rr) syndiotacticity. A combined experimental (synthetic, kinetic, and mechanistic) and theoretical (DFT) investigation has yielded a unimetallic, enantiomorphic-site controlled propagation mechanism. Post-functionalization of the obtained syndiotactic vinyl-functionalized polymers via the thiol-ene click and photocuring reactions readily produced the corresponding thiolated polymers and flexible crosslinked thin film materials, respectively. Complexation of such syndiotactic vinyl-functionalized polymers with isotactic poly(methyl methacrylate) and fullerene C60 generates supramolecular crystalline helical stereocomplexes and inclusion complexes, respectively. Crosslinking of such complexes afforded robust crosslinked stereocomplexes that are solvent resistant and also exhibit considerably enhanced thermal and mechanical properties as compared to the uncrosslinked stereocompexes.

Comparison of Swelling and Mechanical Analysis for the Determination of Crosslink Density of Acrylamide Based Hydrogels Prepared by Ionizing Radiation

International Nuclear Information System (INIS)

Sen, M.

2006-01-01

One of the basic parameters that describes the structure of a hydrogel network is the molecular weight between cross-links or cross-link density of highly swollen network. Several theories have been proposed to calculate the average molecular weight between cross-links. In the highly swollen state, the constrained junction theory indicates that a real network exhibits properties closer to those of the phantom network model and molecular weight between cross-links can be calculated easily by using swelling and polymer-solvent based parameters such as molar volume of the swelling agent, polymer-solvent interaction parameter, functionality, specific volume of the polymer and polymer volume fraction in the relaxed state. Molecular weight between cross-links (M c a ver.) and effective cross-linking density (V e ) of a hydrogel can also be determined from shear modulus data obtained from compression tests. Our previous studies indicated that simple compression analyses and equations derived from Phantom network theory can be used for the determination of effective cross-link density of hydrogels without needing some polymer-solvent based parameters as in the case of swelling based determinations. The M c a ver. and V e values calculated from mechanical tests were found to be very close to the values obtained from swelling experiments. Slight differences observed were attributed to the uncertainty on the value of the χ parameter used in the expression related to swelling data. In this study the uncertainty in the polymer based parameter χ on the M c a ver. was discussed. Poly(acrylamide/methacrylamide) P(AAm/MAAm) and Poly(acrylamide/hydroxyethylmeth acrylate) P(AAm/HEMA) hydrogels were prepared by gamma rays and used as model hydrogel systems. The uniaxial compression was applied to cylindrical samples using the Universal Testing Instrument in the swollen form at pH 7. Stress-strain curves of hydrogels were evaluated to calculate the shear modulus values. The M c a ver

Radiation polymerization and crosslinking: A viable alternative for synthesis of porous functional polymers

Energy Technology Data Exchange (ETDEWEB)

Safrany, Agnes, E-mail: a.safrany@iaea.or [Department of Nuclear Sciences and Applications, International Atomic Energy Agency, P.O. Box 100, A-1400 Vienna (Austria); Beiler, Barbara [Radiation Chemistry Department, Institute of Isotopes, Hungarian Academy of Sciences, P.O. Box 77, H1525 Budapest (Hungary); Vincze, Arpad [Miklos Zrinyi National Defence University, Department of NBC Defence, Budapest 146, P.O. Box 15, H-1581 Budapest (Hungary)

2010-04-15

We have earlier shown the possibility of preparation of crosslinked porous polymers by ionizing radiation-initiated reactions, and here we give an overview of the irradiation conditions-porous properties relationship for several methacrylate type copolymers. We illustrate the possible applications by an environment-friendly chromatographic column using water as eluent and a chemically stable scintillating polymer with excellent ion-binding capacity for possible continuous monitoring of radioactivity in natural waters.

Small Strain Topological Effects of Biopolymer Networks with Rigid Cross-Links

NARCIS (Netherlands)

Zagar, G.; Onck, P. R.; Van der Giessen, E.; Garikipati, K; Arruda, EM

2010-01-01

Networks of cross-linked filamentous biopolymers form topological structures characterized by L, T and X cross-link types of connectivity 2, 3 and 4, respectively. The distribution of cross-links over these three types proofs to be very important for the initial elastic shear stiffness of isotropic

Synthesis, characterization and applications of polymer-metal ...

Indian Academy of Sciences (India)

Abstract. 4-Acryloxy acetophenone was prepared and subjected to suspension polymerization with divinyl- benzene as a cross-linking agent. The resulting network polymer was ligated with benzoyl hydrazone. The functional polymer was treated with metal ions [Cu(II), Fe(II)]. The polymer-metal complexes obtained.

Radiation crosslinking of polymer blends

International Nuclear Information System (INIS)

Spenadel, L.

1979-01-01

Rocked by the one-two punch of rising energy costs and tougher pollution controls, a growing number of companies are looking to radiation crosslinking as a cheaper, cleaner alternative to heat and costly chemical crosslinking agents such as peroxides. With the development of larger, more powerful electron beam machines it is now possible to irradiate parts as thick as 400 mils in a single pass. Two application areas which have been investigated at our laboratory are the electron beam processing of thermoplastic elastomeric automotive parts and EPDM electrical insulation. This paper covers work carried out to develop the necessary technology base for the radiation crosslinking of ethylene propylene/polyolefin blends. Initial results indicate that EP/PE blends of electrical insulation quality cross-link quite readily when irradiated. On the other hand, EP/PP blends developed for automotive fascia require the addition of crosslinking monomers such as trimethylol propane trimethacrylate in order for crosslinking to predominate over chain scission. Crosslinking EP/PP blends improve mar resistance, flexural set and deformation at elevated temperatures. These are all key properties for automotive fascia. (author)

Studies of network organization and dynamics of e-beam crosslinked PVPs: From macro to nano

International Nuclear Information System (INIS)

Dispenza, C.; Grimaldi, N.; Sabatino, M.-A.; Todaro, S.; Bulone, D.; Giacomazza, D.; Przybytniak, G.; Alessi, S.; Spadaro, G.

2012-01-01

In this work the influence of poly(N-vinyl pyrrolidone) (PVP) concentration in water on the organization and dynamics of the corresponding macro-/nanogel networks has been systematically investigated. Irradiation has been performed at the same irradiation dose (within the sterilization dose range) and dose rate. In the selected irradiation conditions, the transition between macroscopic gelation and micro-/nanogels formation is observed just below the critical overlap concentration (∼1 wt%), whereas the net prevalence of intra-molecular over inter-molecular crosslinking occurs at a lower polymer concentration (below 0.25 wt%). Dynamic–mechanical spectroscopy has been applied as a classical methodology to estimate the network mesh size for macrogels in their swollen state, while 13 C NMR spin–lattice relaxation spectroscopy has been applied on both the macrogel and nanogel freeze dried residues to withdraw interesting information of the network spatial organization in the passage of scale from macro to nano. - Highlights: ► Aqueous solutions of commercial PVP were irradiated using linear electron accelerator. ► By varying polymer concentration it is possible to obtain information from macro to nano networks. ► Spin–lattice relaxation times are associated to the mobility of molecular segments. ► 1 H– 13 C-NMR proton relaxation time represents a junction between macro/nano world.

Entanglement effects in model polymer networks

Science.gov (United States)

Everaers, R.; Kremer, K.

The influence of topological constraints on the local dynamics in cross-linked polymer melts and their contribution to the elastic properties of rubber elastic systems are a long standing problem in statistical mechanics. Polymer networks with diamond lattice connectivity (Everaers and Kremer 1995, Everaers and Kremer 1996a) are idealized model systems which isolate the effect of topology conservation from other sources of quenched disorder. We study their behavior in molecular dynamics simulations under elongational strain. In our analysis we compare the measured, purely entropic shear moduli G to the predictions of statistical mechanical models of rubber elasticity, making extensive use of the microscopic structural and topological information available in computer simulations. We find (Everaers and Kremer 1995) that the classical models of rubber elasticity underestimate the true change in entropy in a deformed network significantly, because they neglect the tension along the contour of the strands which cannot relax due to entanglements (Everaers and Kremer (in preparation)). This contribution and the fluctuations in strained systems seem to be well described by the constrained mode model (Everaers 1998) which allows to treat the crossover from classical rubber elasticity to the tube model for polymer networks with increasing strand length within one transparant formalism. While this is important for the description of the effects we try to do a first quantitative step towards their explanation by topological considerations. We show (Everaers and Kremer 1996a) that for the comparatively short strand lengths of our diamond networks the topology contribution to the shear modulus is proportional to the density of entangled mesh pairs with non-zero Gauss linking number. Moreover, the prefactor can be estimated consistently within a rather simple model developed by Vologodskii et al. and by Graessley and Pearson, which is based on the definition of an entropic

Synthesis and characterization of poly (n-butyl acrylate)-poly (methyl methacrylate) latex interpenetrating polymer networks by radiation-induced seeded emulsion polymerization

Energy Technology Data Exchange (ETDEWEB)

Yu Haibo [Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Peng Jing [Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China)], E-mail: jpeng@pku.edu.cn; Zhai Maolin; Li Jiuqiang; Wei Genshuan [Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); Qiao Jinliang [Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China); SINOPEC Beijing Research Institute of Chemical Industry, Beijing 100013 (China)

2007-11-15

A series of latex interpenetrating polymer networks (LIPNs) were prepared via a two-stage emulsion polymerization of methyl methacrylate (MMA) or mixture of MMA and n-butyl acrylate (n-BA) on crosslinked poly(n-butyl acrylate)(PBA) seed latex using {sup 60}Co {gamma}-ray radiation. The particles of resultant latex were produced with diameters between 150 and 250 nm. FTIR spectra identified the formation of crosslinked copolymers of PMMA or P(MMA-co-BA). Dynamic light scattering (DLS) showed that with increasing n-BA concentration in second-stage monomers, the particle size of LIPN increased. Transmission electron microscope(TEM) photographs showed that the morphology of resultant acrylate interpenetrating polymer network (IPN) latex varied from the distinct core-shell structure to homogenous particle structure with the increase of n-BA concentration, and the morphology was mainly controlled by the miscibility between crosslinked PBA seed and second-stage copolymers and polarity of P(MMA-co-BA)copolymers. In addition, differential scanning calorimeter (DSC) measurements indicated the existence of reinforced miscibility between PBA seed and P(MMA-co-BA)copolymer in prepared LIPNs.

Core Cross-Linked Multiarm Star Polymers with Aggregation-Induced Emission and Temperature Responsive Fluorescence Characteristics

KAUST Repository

Zhang, Zhen

2017-05-19

Aggregation-induced emission (AIE) active core cross-linked multiarm star polymers, carrying polystyrene (PS), polyethylene (PE), or polyethylene-b-polycaprolactone (PE-b-PCL) arms, have been synthesized through an “arm-first” strategy, by atom transfer radical copolymerization (ATRP) of a double styrene-functionalized tetraphenylethene (TPE-2St) used as a cross-linker with linear arm precursors possessing terminal ATRP initiating moieties. Polyethylene macroinitiator (PE–Br) was prepared via the polyhomologation of dimethylsulfoxonium methylide with triethylborane followed by oxidation/hydrolysis and esterification of the produced PE–OH with 2-bromoisobutyryl bromide; polyethylene-block-poly(ε-caprolactone) diblock macroinitiator was derived by combining polyhomologation with ring-opening polymerization (ROP). All synthesized star polymers showed AIE-behavior either in solution or in bulk. At high concentration in good solvents (e.g., THF, or toluene) they exhibited low photoluminescence (PL) intensity due to the inner filter effect. In sharp contrast to the small molecule TPE-2St, the star polymers were highly emissive in dilute THF solutions. This can be attributed to the cross-linked structure of poly(TPE-2St) core which restricts the intramolecular rotation and thus induces emission. In addition, the PL intensity of PE star polymers in THF(solvent)/n-hexane(nonsolvent) mixtures, due to their nearly spherical shape, increased when the temperature decreased from 55 to 5 °C with a linear response in the range 40–5 °C.

Silk Fibroin/Polyvinyl Pyrrolidone Interpenetrating Polymer Network Hydrogels

Directory of Open Access Journals (Sweden)

Dajiang Kuang

2018-02-01

Full Text Available Silk fibroin hydrogel is an ideal model as biomaterial matrix due to its excellent biocompatibility and used in the field of medical polymer materials. Nevertheless, native fibroin hydrogels show poor transparency and resilience. To settle these drawbacks, an interpenetrating network (IPN of hydrogels are synthesized with changing ratios of silk fibroin/N-Vinyl-2-pyrrolidonemixtures that crosslink by H2O2 and horseradish peroxidase. Interpenetrating polymer network structure can shorten the gel time and the pure fibroin solution gel time for more than a week. This is mainly due to conformation from the random coil to the β-sheet structure changes of fibroin. Moreover, the light transmittance of IPN hydrogel can be as high as more than 97% and maintain a level of 90% within a week. The hydrogel, which mainly consists of random coil, the apertures inside can be up to 200 μm. Elastic modulus increases during the process of gelation. The gel has nearly 95% resilience under the compression of 70% eventually, which is much higher than native fibroin gel. The results suggest that the present IPN hydrogels have excellent mechanical properties and excellent transparency.

Fabrication of Si negative electrodes for Li-ion batteries (LIBs) using cross-linked polymer binders.

Science.gov (United States)

Jang, Suk-Yong; Han, Sien-Ho

2016-12-19

Currently, Si as an active material for LIBs has been attracting much attention due to its high theoretical specific capacity (3572 mAh g -1 ). However, a disadvantage when using a Si negative electrode for LIBs is the abrupt drop of its capabilities during the cycling process. Therefore, there have been a few studies of polymers such as poly(vinylidene fluoride) (PVdF), carboxymethyl cellulose (CMC), styrene butadiene rubber (SBR) and polyacrylic acid (PAA) given that the robust structure of a polymeric binder to LIBs anodes is a promising means by which to enhance the performance of high-capacity anodes. These studies essentially focused mainly on modifying of the linear-polymer component or on copolymers dissolved in solvents. Cross-linking polymers as a binder may be preferred due to their good scratch resistance, excellent chemical resistance and high levels of adhesion and resilience. However, because these types of polymers (with a rigid structure and cross-linking points) are also insoluble in general organic solvents, applying these types in this capacity is virtually impossible.

Semi-Interpenetrating polymer network hydrogels based on aspen hemicellulose and chitosan: Effect of crosslinking sequence on hydrogel properties

Science.gov (United States)

Muzaffer Ahmet Karaaslan; Mandla A. Tshabalala; Gisela Buschle-Diller

2012-01-01

Semi-interpenetrating network hydrogel films were prepared using hemicellulose and chemically crosslinked chitosan. Hemicellulose was extracted from aspen by using a novel alkaline treatment and characterized by HPSEC, and consisted of a mixture of high and low molecular weight polymeric fractions. HPLC analysis of the acid hydrolysate of the hemicellulose showed that...

Theory of liquid crystal elastomers and polymer networks : Connection between neoclassical theory and differential geometry.

Science.gov (United States)

Nguyen, Thanh-Son; Selinger, Jonathan V

2017-09-01

In liquid crystal elastomers and polymer networks, the orientational order of liquid crystals is coupled with elastic distortions of crosslinked polymers. Previous theoretical research has described these materials through two different approaches: a neoclassical theory based on the liquid crystal director and the deformation gradient tensor, and a geometric elasticity theory based on the difference between the actual metric tensor and a reference metric. Here, we connect those two approaches using a formalism based on differential geometry. Through this connection, we determine how both the director and the geometry respond to a change of temperature.

Preliminary investigation of the NMR, optical and x-ray CT dose-response of polymer gel dosimeters with cosolvents and increased crosslinker levels

International Nuclear Information System (INIS)

Koeva, V I; McAuley, K B; Jirasek, A; Schreiner, L J

2009-01-01

Three co-solvents (glycerol, N-propanol and isopropanol) have been investigated for increasing the solubility of N,N'-methylene-bisacrylamide (Bis) crosslinker in polymer gel dosimeter recipes. Using isopropanol, the crosslinker solubility increased from approximately from 3 to 10% by weight, enabling the manufacture of polymer gel dosimeters with higher levels of crosslinking than was previously possible. The new dosimeter recipes can be imaged effectively using Nuclear Magnetic Resonance (NMR), optical and x-ray Computed Tomography (CT) techniques.

Preliminary investigation of the NMR, optical and x-ray CT dose-response of polymer gel dosimeters with cosolvents and increased crosslinker levels

Energy Technology Data Exchange (ETDEWEB)

Koeva, V I; McAuley, K B [Chemical Engineering Department, Queen' s University, Kingston, K7L 3N6 (Canada); Jirasek, A [Department of Physics and Astronomy, University of Victoria, Victoria, V8W 6V5 (Canada); Schreiner, L J [Cancer Centre of Southeastern Ontario, Kingston, K7L 5P9 (Canada)], E-mail: Kim.McAuley@chee.queensu.ca

2009-05-01

Three co-solvents (glycerol, N-propanol and isopropanol) have been investigated for increasing the solubility of N,N'-methylene-bisacrylamide (Bis) crosslinker in polymer gel dosimeter recipes. Using isopropanol, the crosslinker solubility increased from approximately from 3 to 10% by weight, enabling the manufacture of polymer gel dosimeters with higher levels of crosslinking than was previously possible. The new dosimeter recipes can be imaged effectively using Nuclear Magnetic Resonance (NMR), optical and x-ray Computed Tomography (CT) techniques.

Redundancy and cooperativity in the mechanics of compositely crosslinked filamentous networks.

Directory of Open Access Journals (Sweden)

Moumita Das

Full Text Available The cytoskeleton of living cells contains many types of crosslinkers. Some crosslinkers allow energy-free rotations between filaments and others do not. The mechanical interplay between these different crosslinkers is an open issue in cytoskeletal mechanics. Therefore, we develop a theoretical framework based on rigidity percolation to study a generic filamentous system containing both stretching and bond-bending forces to address this issue. The framework involves both analytical calculations via effective medium theory and numerical simulations on a percolating triangular lattice with very good agreement between both. We find that the introduction of angle-constraining crosslinkers to a semiflexible filamentous network with freely rotating crosslinks can cooperatively lower the onset of rigidity to the connectivity percolation threshold-a result argued for years but never before obtained via effective medium theory. This allows the system to ultimately attain rigidity at the lowest concentration of material possible. We further demonstrate that introducing angle-constraining crosslinks results in mechanical behaviour similar to just freely rotating crosslinked semflexible filaments, indicating redundancy and universality. Our results also impact upon collagen and fibrin networks in biological and bio-engineered tissues.

Nanomechanics of layer-by-layer polyelectrolyte complexes: a manifestation of ionic cross-links and fixed charges.

Science.gov (United States)

Han, Biao; Chery, Daphney R; Yin, Jie; Lu, X Lucas; Lee, Daeyeon; Han, Lin

2016-01-28

This study investigates the roles of two distinct features of ionically cross-linked polyelectrolyte networks - ionic cross-links and fixed charges - in determining their nanomechanical properties. The layer-by-layer assembled poly(allylamine hydrochloride)/poly(acrylic acid) (PAH/PAA) network is used as the model material. The densities of ionic cross-links and fixed charges are modulated through solution pH and ionic strength (IS), and the swelling ratio, elastic and viscoelastic properties are quantified via an array of atomic force microscopy (AFM)-based nanomechanical tools. The roles of ionic cross-links are underscored by the distinctive elastic and viscoelastic nanomechanical characters observed here. First, as ionic cross-links are highly sensitive to solution conditions, the instantaneous modulus, E0, exhibits orders-of-magnitude changes upon pH- and IS-governed swelling, distinctive from the rubber elasticity prediction based on permanent covalent cross-links. Second, ionic cross-links can break and self-re-form, and this mechanism dominates force relaxation of PAH/PAA under a constant indentation depth. In most states, the degree of relaxation is >90%, independent of ionic cross-link density. The importance of fixed charges is highlighted by the unexpectedly more elastic nature of the network despite low ionic cross-link density at pH 2.0, IS 0.01 M. Here, the complex is a net charged, loosely cross-linked, where the degree of relaxation is attenuated to ≈50% due to increased elastic contribution arising from fixed charge-induced Donnan osmotic pressure. In addition, this study develops a new method for quantifying the thickness of highly swollen polymer hydrogel films. It also underscores important technical considerations when performing nanomechanical tests on highly rate-dependent polymer hydrogel networks. These results provide new insights into the nanomechanical characters of ionic polyelectrolyte complexes, and lay the ground for further

Mechanically Strong, Polymer Cross-linked Aerogels (X-Aerogels)

Science.gov (United States)

Leventis, Nicholas

2006-01-01

Aerogels comprise a class of low-density, high porous solid objects consisting of dimensionally quasi-stable self-supported three-dimensional assemblies of nanoparticles. Aerogels are pursued because of properties above and beyond those of the individual nanoparticles, including low thermal conductivity, low dielectric constant and high acoustic impedance. Possible applications include thermal and vibration insulation, dielectrics for fast electronics, and hosting of functional guests for a wide variety of optical, chemical and electronic applications. Aerogels, however, are extremely fragile materials, hence they have found only limited application in some very specialized environments, for example as Cerenkov radiation detectors in certain types of nuclear reactors, aboard spacecraft as collectors of hypervelocity particles (refer to NASA's Stardust program) and as thermal insulators on planetary vehicles on Mars (refer to Sojourner Rover in 1997 and Spirit and Opportunity in 2004). Along these lines, the X-Aerogel is a new NASA-developed strong lightweight material that has resolved the fragility problem of traditional (native) aerogels. X-Aerogels are made by applying a conformal polymer coating on the surfaces of the skeletal nanoparticles of native aerogels (see Scanning Electron Micrographs). Since the relative amounts of the polymeric crosslinker and the backbone are comparable, X-Aerogels can be viewed either as aerogels modified by the templated accumulation of polymer on the skeletal nanoparticles, or as nanoporous polymers made by remplated casting of polymer on a nanostructured framework. The most striking feature of X-Aerogels is that for a nominal 3-fold increase in density (still a ultralighweight material), the mechanical strength can be up to 300 times higher than the strength of the underlying native aerogel. Thus, X-Aerogels combine a multiple of the specific compressive strength of steel, with the the thermal conductivity of styrofoam. X

Concept of polymer alloy electrolytes: towards room temperature operation of lithium-polymer batteries

International Nuclear Information System (INIS)

Noda, Kazuhiro; Yasuda, Toshikazu; Nishi, Yoshio

2004-01-01

Polymer alloy technique is very powerful tool to tune the ionic conductivity and mechanical strength of polymer electrolyte. A semi-interpenetrating polymer network (semi-IPN) polymer alloy electrolyte, composed of non-cross-linkable siloxane-based polymer and cross-linked 3D network polymer, was prepared. Such polymer alloy electrolyte has quite high ionic conductivity (more than 10 -4 Scm -1 at 25 o C and 10 -5 Scm -1 at -10 o C) and mechanical strength as a separator film with a wide electrochemical stability window. A lithium metal/semi-IPN polymer alloy solid state electrolyte/LiCoO 2 cell demonstrated promising cycle performance with room temperature operation of the energy density of 300Wh/L and better rate performance than conventional PEO based lithium polymer battery ever reported

Poly(tetramethyleneterephthalate) crosslinked by irradiation

International Nuclear Information System (INIS)

Nyberg, D.D.

1978-01-01

Crosslinking, e.g., by irradiation, of a polymer comprising poly(tetramethyleneterephthalate) is made possible by the addition of a member selected from the group consisting of triallyl cyanurate and N,N'-m-phenylenedimaleimide. The resulting crosslinked modified polymer may be rendered heat recoverable

Epoxy Crosslinked Silica Aerogels (X-Aerogels)

Science.gov (United States)

fabrizio, Eve; Ilhan, Faysal; Meador, Mary Ann; Johnston, Chris; Leventis, Nicholas

2004-01-01

NASA is interested in the development of strong lightweight materials for the dual role of thermal insulator and structural component for space vehicles; freeing more weight for useful payloads. Aerogels are very-low density materials (0.010 to 0.5 g/cc) that, due to high porosity (meso- and microporosity), can be, depending on the chemical nature of the network, ideal thermal insulators (thermal conductivity approx. 15 mW/mK). However, aerogels are extremely fragile. For practical application of aerogels, one must increase strength without compromising the physical properties attributed to low density. This has been achieved by templated growth of an epoxy polymer layer that crosslinks the "pearl necklace" network of nanoparticles: the framework of a typical silica aerogel. The requirement for conformal accumulation of the epoxy crosslinker is reaction both with the surface of silica and with itself. After cross-linking, the strength of a typical aerogel monolith increases by a factor of 200, in the expense of only a 2-fold increase in density. Strength is increased further by coupling residual unreacted epoxides with diamine.

The polymerization of furfuryl alcohol with p-toluenesulfonic acid: photo cross-linkable feature of the polymer

International Nuclear Information System (INIS)

Principe, Martha; Martinez, Ricardo; Ortiz, Pedro; Rieumont, Jacques

2000-01-01

Poly (furfuryl alcohol) with different amounts of oxymethylenic bridges was synthesized using trifluoroacetic and p-toluenesulfonic acid. All polymers displayed a tendency to retain acids. The isolated products containing traces of acid became insoluble in a few hours; while neutral material maintains theirs solubility for at least one month. Polymers stored in solution were stable according to their HNMR spectra. Polymers cross-linked after being exposed to UV radiation. The product of the reaction of polymer with maleic anhydride is useful for preparing negative photo resists. (author)

Anion exchange membranes based on terminally crosslinked methyl morpholinium-functionalized poly(arylene ether sulfone)s

Science.gov (United States)

Kwon, Sohyun; Rao, Anil H. N.; Kim, Tae-Hyun

2018-01-01

Azide-assisted terminal crosslinking of methyl morpholinium-functionalized poly(arylene ether sulfone) block copolymers yields products (xMM-PESs) suitable for use as anion exchange membranes. By combining the advantages of bulky morpholinium conductors and our unique polymer network crosslinked only at the termini of the polymer chains, we can produce AEMs that after the crosslinking show minimal loss in conductivity, yet with dramatically reduced water uptake. Terminal crosslinking also significantly increases the thermal, mechanical and chemical stability levels of the membranes. A high ion conductivity of 73.4 mS cm-1 and low water uptake of 26.1% at 80 °C are obtained for the crosslinked membrane with higher amount of hydrophilic composition, denoted as xMM-PES-1.5-1. In addition, the conductivity of the crosslinked xMM-PES-1.5-1 membrane exceeds that of its non-crosslinked counterpart (denoted as MM-PES-1.5-1) above 60 °C at 95% relative humidity because of its enhanced water retention capacity caused by the terminally-crosslinked structure.

Shrink properties of crosslinked polymers as investigated by a novel method

International Nuclear Information System (INIS)

Dobo, J.; Forgacs, P.; Somogyi, A.

1981-01-01

In the production and use of shrink materials, the slightly radiation crosslinked polymers are repeatedly heated above and cooled below their melting point, while maintained in extended state. Their shrink properties were investigated by model experiments simulating the thermal and mechanical influences. First an Instron testing apparatus has been used. In this paper, results obtained with a home-made electronic dynamometer with programmable extension and programmable temperature control are reported. (author)

Core Cross-Linked Multiarm Star Polymers with Aggregation-Induced Emission and Temperature Responsive Fluorescence Characteristics

KAUST Repository

Zhang, Zhen; Bilalis, Panagiotis; Zhang, Hefeng; Gnanou, Yves; Hadjichristidis, Nikolaos

2017-01-01

Aggregation-induced emission (AIE) active core cross-linked multiarm star polymers, carrying polystyrene (PS), polyethylene (PE), or polyethylene-b-polycaprolactone (PE-b-PCL) arms, have been synthesized through an “arm-first” strategy, by atom

Multi-functionalized side-chain supramolecular polymers: A methodology towards tunable functional materials

Science.gov (United States)

Nair, Kamlesh Prabhakaran

Even as we see a significant growth in the field of supramolecular polymers in the last ten years, multi-functionalized systems have been scarcely studied. Noncovalent multi-functionalization provides unique advantages such as rapid materials optimization via reversible functionalization as well as for the tuning of materials properties by exploiting the differences in the nature of these reversible interactions. This thesis involves the design principles, synthesis & methodology of supramolecular side-chain multi-functionalized polymers. The combination of a functionally tolerant & controlled polymerization technique such as ROMP with multiple noncovalent interactions such as hydrogen bonding, metal coordination and ionic interactions has been successfully used to synthesize these polymers. Furthermore, the orthogonality between the above interactions in block/random copolymers has been studied in detail. It has been found that the studied interactions were orthogonal to each other. To validate the viability of this methodology using multiple orthogonal interactions towards materials design noncovalent crosslinking of polymers has been used as a potential application. Three classes of networks have been studied: complementary multiple hydrogen bonded networks, metal crosslinked networks, & multi-functionalized hydrogen bonded and metal coordinated networks. The first room temperature decrosslinking by exclusive complementary hydrogen bonded interactions has been successfully achieved. Furthermore network properties have been successfully tuned by varying the network micro-structure which in turn was tuned by the hydrogen bonding motifs used for inter-chain crosslinking. By combining two different noncovalent interactions used for inter-chain crosslinking, it was possible to make multi-functionalized materials whose properties could be controlled by varying the crosslinking strategy. Hence by employing multi-functionalization methodology, important materials

Radiation-induced crosslinking of aromatic polymers with cardo group

International Nuclear Information System (INIS)

Xu Jun; Zhang Wanxi

1991-01-01

The effects of irradiation on the aromatic polymers with cardo group, such as polyetherketone with cardo group (PEK-C) and polyethersulfone with cardo group (PES-C) were studied. It was found that PEK-C and PES-C can be crosslinked by irradiation under vacuum. Moreover, it was also found that the intensity of the shake-up peak of X-ray photoelectron spectroscopy (XPS) for PEK-C and PES-C varies as irradiation dose. Gelation doses (Rg) of PEK-C and PES-C were estimated by shake-up peaks of XPS. (author) 6 refs.; 8 figs.; 3 tabs

Competing dynamic phases of active polymer networks

Science.gov (United States)

Freedman, Simon; Banerjee, Shiladitya; Dinner, Aaron R.

Recent experiments on in-vitro reconstituted assemblies of F-actin, myosin-II motors, and cross-linking proteins show that tuning local network properties can changes the fundamental biomechanical behavior of the system. For example, by varying cross-linker density and actin bundle rigidity, one can switch between contractile networks useful for reshaping cells, polarity sorted networks ideal for directed molecular transport, and frustrated networks with robust structural properties. To efficiently investigate the dynamic phases of actomyosin networks, we developed a coarse grained non-equilibrium molecular dynamics simulation of model semiflexible filaments, molecular motors, and cross-linkers with phenomenologically defined interactions. The simulation's accuracy was verified by benchmarking the mechanical properties of its individual components and collective behavior against experimental results at the molecular and network scales. By adjusting the model's parameters, we can reproduce the qualitative phases observed in experiment and predict the protein characteristics where phase crossovers could occur in collective network dynamics. Our model provides a framework for understanding cells' multiple uses of actomyosin networks and their applicability in materials research. Supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship (NDSEG) Program.

Models for stiffening in cross-linked biopolymer networks : A comparative study

NARCIS (Netherlands)

van Dillen, T.; Onck, P. R.; Van der Giessen, E.

In a recent publication, we studied the mechanical stiffening behavior in two-dimensional (2D) cross-linked networks of semiflexible biopolymer filaments under simple shear [Onck, P.R., Koeman, T., Van Dillen, T., Van der Giessen, E., 2005. Alternative explanation of stiffening in cross-linked

Proton conducting semi-IPN based on Nafion and crosslinked poly(AMPS) for direct methanol fuel cell

International Nuclear Information System (INIS)

Cho, Ki-Yun; Jung, Ho-Young; Shin, Seung-Shik; Choi, Nam-Soon; Sung, Shi-Joon; Park, Jung-Ki; Choi, Jong-Ho; Park, Kyung-Won; Sung, Yung-Eun

2004-01-01

For direct methanol fuel cell, the proton conducting membrane based on semi-interpenetrating polymer networks (IPNs) of Nafion and crosslinked poly(AMPS) was prepared and characterized. The modification of Nafion with crosslinked poly(AMPS) such as hydrocarbon polymer changed the state of water in membranes. Without a significant increase of the membrane resistance, the semi-IPNs demonstrated a reduction of the methanol permeability, comparing to the native Nafion. And the maximum power density of AMPS60 increased as much as 22.2% compared with Nafion

Interpenetrated polymer networks based on commercial silicone elastomers and ionic networks with high dielectric permittivity and self-healing properties

DEFF Research Database (Denmark)

Ogliani, Elisa; Yu, Liyun; Skov, Anne Ladegaard

the applicability. One method used to avoid this limitation is to increase the dielectric permittivity of the material in order to improve the actuation response at a given field. Recently, interpenetrating polymer networks (IPNs) based on covalently cross-linked commercial silicone elastomers and ionic networks...... from amino- and carboxylic acid- functional silicones have been designed[2] (Figure 1). This novel system provides both the mechanical stability and the high breakdown strength given by the silicone part of the IPNs and the high permittivity and the softening effect of the ionic network. Thus......,1 Hz), and the commercial elastomers RT625 and LR3043/30 provide thebest viscoelastic properties to the systems, since they maintain low viscous losses upon addition of ionic network. The values ofthe breakdown strength in all cases remain higher than that of the reference pure PDMS network (ranging...

Shape memory and actuation behavior of semicrystalline polymer networks

Energy Technology Data Exchange (ETDEWEB)

Bothe, Martin

2014-07-01

Shape memory polymers (SMPs) can change their shape on application of a suitable stimulus. To enable such behavior, a 'programming' procedure fixes a deformation, yielding a stable temporary shape. In thermoresponsive SMPs, subsequent heating triggers entropy-elastic recovery of the initial shape. An additional shape change on cooling, i.e. thermoreversible two-way actuation, can be stimulated by a crystallization phenomenon. In this thesis, cyclic thermomechanical measurements systematically determined (1) the shape memory and (2) the actuation behavior under constant load as well as under stress-free conditions. Chemically cross-linked, star-shaped polyhedral oligomeric silsesquioxane polyurethane (SPOSS-PU) hybrid polymer networks and physically cross-linked poly(ester urethane) (PEU) block copolymers were investigated around the melting and crystallization temperatures of their polyester soft segments. (1) The SPOSS-PUs showed excellent shape fixities and recoverabilities of almost 100% at high cross-linking density, while PEUs exhibited pronounced shape memory properties at increased soft segment content. Furthermore, two-fold programmed SPOSS-PU specimens were able to recover their initial shape in two thermally separated events. Even a neck, which formed during deformation of SPOSS-PUs with high soft segment content, was reversed. (2) In PEUs, globally oriented crystallization on cooling drove expansion of the sample, in particular at high soft segment content and after application of a strong deformation. Melting reversed that orientation; the PEU sample contracted and thereby completed the thermoreversible actuation cycle. Under load, multiple polymorphic phase transitions enabled two successive expansion and contraction steps, while under stress-free conditions various geometric shape changes, including the increase and decrease of PEU sample length and thickness as well as twisting and untwisting could be experimentally witnessed. Such

Shape memory and actuation behavior of semicrystalline polymer networks

International Nuclear Information System (INIS)

Bothe, Martin

2014-01-01

Shape memory polymers (SMPs) can change their shape on application of a suitable stimulus. To enable such behavior, a 'programming' procedure fixes a deformation, yielding a stable temporary shape. In thermoresponsive SMPs, subsequent heating triggers entropy-elastic recovery of the initial shape. An additional shape change on cooling, i.e. thermoreversible two-way actuation, can be stimulated by a crystallization phenomenon. In this thesis, cyclic thermomechanical measurements systematically determined (1) the shape memory and (2) the actuation behavior under constant load as well as under stress-free conditions. Chemically cross-linked, star-shaped polyhedral oligomeric silsesquioxane polyurethane (SPOSS-PU) hybrid polymer networks and physically cross-linked poly(ester urethane) (PEU) block copolymers were investigated around the melting and crystallization temperatures of their polyester soft segments. (1) The SPOSS-PUs showed excellent shape fixities and recoverabilities of almost 100% at high cross-linking density, while PEUs exhibited pronounced shape memory properties at increased soft segment content. Furthermore, two-fold programmed SPOSS-PU specimens were able to recover their initial shape in two thermally separated events. Even a neck, which formed during deformation of SPOSS-PUs with high soft segment content, was reversed. (2) In PEUs, globally oriented crystallization on cooling drove expansion of the sample, in particular at high soft segment content and after application of a strong deformation. Melting reversed that orientation; the PEU sample contracted and thereby completed the thermoreversible actuation cycle. Under load, multiple polymorphic phase transitions enabled two successive expansion and contraction steps, while under stress-free conditions various geometric shape changes, including the increase and decrease of PEU sample length and thickness as well as twisting and untwisting could be experimentally witnessed. Such actuation

Free-radical-induced chain scission and cross-linking of polymers in aqueous solution. An overview

International Nuclear Information System (INIS)

Von Sonntag, C.

2002-01-01

Complete text of publication follows. In the radiolysis of N 2 O-saturated aqueous solutions OH are generated. In their reactions with polymers, they give rise to polymer-derived radicals. The kinetics of the formation and decay of these radicals are reviewed. The rate of reaction of a polymer with a reactive free radical is noticeably lower than that of an equivalent concentration of monomer due to the non-random distribution of the reaction sites. Once a larger number of radicals are formed on one polymer molecule, e.g. upon pulse radiolysis, close-by radicals recombine more rapidly while the more distant ones survive for much longer times than an equivalent concentration of freely diffusing radicals. Intermolecular cross-linking (between two polymer chains, increase in molecular weight) and intramolecular cross-linking (formation of small loops, no increase in polymer weight) are competing processes, and their relative yields thus depend on the dose rate and polymer concentration. Hydrogen-transfer reactions within the polymer, e.g. transformation of a secondary radical into a tertiary one, are common and facilitated by the high local density of reactive sites. Due to repulsive forces, the lifetime of radicals of charged polymers is substantially increased. This enables even relatively slow b-fragmentation reactions to become of importance. In the case of poly(methacrylic acid), where β-fragmentation is comparatively fast, this even leads to an unzipping, and as a consequence of the efficient release of methacrylic acid the situation of equilibrium polymerization is approached. Heterolytic β-fragmentation is possible when adequate leaving groups are available, e.g. in polynucleotides and DNA. In the presence of O 2 , chain scission occurs via oxyl radicals as intermediates. Some implications for technical applications are discussed

Application of polymers cross-linked by electron beam irradiation to electric wire industry

International Nuclear Information System (INIS)

Oda, Eisuke

1976-01-01

Applications of the polymers cross-linked by electron beam irradiation to electric wire industry as an example of dully developed utilization are reviewed. The report is divided into five parts, namely 1) radiation sources and irradiation processes, 2) development of crosslinking materials, 3) accumulation of electric charge and accumulation of heat, 4) examples of application, and 5) future prospect. Such a phenomenon as discharge destruction pattern (Lichtenberg figure) must be solved, when cable insulation materials are cross-linked by electron beam irradiation. The measures for preventing the discharge destruction are required, especially when the layers of polyethylene insulation for high voltage cables are irradiated. The accumulation of heat causes the troubles in foaming, degeneration and wire running of high potential cables, when the layers of insulation are thick. Effective promoters for cross-linking must be studied to reduce the radiation dose. The irradiators capable of irradiating wires uniformly are desirable. Electron beam accelerators will be used, as far as the radiation dose of 10 or more Mrad is required for cross-linking irradiation. If the dose of one tenth or less of the above value is required, gamma-ray sources (RI) are rather easily applicable than focused strong beam. The utilization of spent nuclear fuel is desirable. (Iwakiri, K.)

Gelation Behavior Study of a Resorcinol–Hexamethyleneteramine Crosslinked Polymer Gel for Water Shut-Off Treatment in Low Temperature and High Salinity Reservoirs

Directory of Open Access Journals (Sweden)

Yongpeng Sun

2017-07-01

Full Text Available Mature oilfields usually encounter the problem of high watercut. It is practical to use chemical methods for water-shutoff in production wells, however conventional water-shutoff agents have problems of long gelation time, low gel strength, and poor stability under low temperature and high salinity conditions. In this work a novel polymer gel for low temperature and high salinity reservoirs was developed. This water-shutoff agent had controllable gelation time, adjustable gel strength and good stability performance. The crosslinking process of this polymer gel was studied by rheological experiments. The process could be divided into an induction period, a fast crosslinking period, and a stable period. Its gelation behaviors were investigated in detail. According to the Gel Strength Code (GSC and vacuum breakthrough method, the gel strength was displayed in contour maps. The composition of the polymer gel was optimized to 0.25~0.3% YG100 + 0.6~0.9% resorcinol + 0.2~0.4% hexamethylenetetramine (HMTA + 0.08~0.27% conditioner (oxalic acid. With the concentration increase of the polymer gel and temperature, the decrease of pH, the induction period became shorter and the crosslinking was more efficient, resulting in better stability performance. Various factors of the gelation behavior which have an impact on the crosslinking reaction process were examined. The relationships between each impact factor and the initial crosslinking time were described with mathematical equations.

Nanoporous polymer electrolyte

Science.gov (United States)

Elliott, Brian [Wheat Ridge, CO; Nguyen, Vinh [Wheat Ridge, CO

2012-04-24

A nanoporous polymer electrolyte and methods for making the polymer electrolyte are disclosed. The polymer electrolyte comprises a crosslinked self-assembly of a polymerizable salt surfactant, wherein the crosslinked self-assembly includes nanopores and wherein the crosslinked self-assembly has a conductivity of at least 1.0.times.10.sup.-6 S/cm at 25.degree. C. The method of making a polymer electrolyte comprises providing a polymerizable salt surfactant. The method further comprises crosslinking the polymerizable salt surfactant to form a nanoporous polymer electrolyte.

Covalent Crosslinking of Porous Poly(Ionic Liquid) Membrane via a Triazine Network

OpenAIRE

Täuber, Karoline; Dani, Alessandro; Yuan, Jiayin

2017-01-01

Porous poly(ionic liquid) membranes that were prepared via electrostatic cross-linking were subsequently covalently cross-linked via formation of a 1,3,5-triazine network. The additional covalent cross-links do not affect the pore size and pore size distribution of the membranes and stabilize them towards salt solutions of high ionic strength, enabling the membranes to work in a broader environmental window.

Polycaprolactone diacrylate crosslinked biodegradable semi-interpenetrating networks of polyacrylamide and gelatin for controlled drug delivery

International Nuclear Information System (INIS)

Jaiswal, Maneesh; Koul, Veena; Dinda, Amit K; Gupta, Asheesh

2010-01-01

A biodegradable semi-interpenetrating hydrogel network (semi-IPN) of polyacrylamide and gelatin was prepared using polycaprolactone diacrylate (mol. wt ∼ 640) as a crosslinker. The drug-polymer interaction and IPN formation were investigated by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and thermal gravimetric analysis (TGA). Scanning electron micrographs of lyophilized matrices revealed porous internal structure with varying pore sizes under equilibrium hydrated conditions, depending upon formulation composition. pH-dependent swelling and degradation was enhanced with increasing gelatin content and decreasing crosslinker concentration (Cs). Compression modulus (CM) (at 20% strain) increased significantly from 23 ± 1.4 to 75 ± 2.7 kPa (p 0 C). Fitting of drug release data in the Korsmeyer-Peppas model suggested sustained release behavior up to 10 days with a combination of diffusion and erosion mechanism (0.5 t /M ∞ ≤ 0.6). The newly developed porous, biodegradable and elastic semi-IPNs may serve as an ideal matrix for controlled drug release and wound healing applications. The possibilities can be explored for pharmaceutical and tissue engineering applications.

Influences of poly (vinyl alcohol molecular weight and carbon nanotubes on radiation crosslinking shape memory polymers

Directory of Open Access Journals (Sweden)

Aamer A.M. Alfayyadh

2017-06-01

Full Text Available Polyvinyl alcohol (PVA of two molecular weights was used to prepare shape memory polymers based on chemical-crosslinking by glutaraldehyde. The chemical-crosslinking was done in the presence of 2-carboxyethyl acrylate oligomers (CEA and nano-filler [multi-wall carbon nanotubes (MWCNT and functionalized carbon nanotubes (MWCNT-NH2] followed by radiation-induced crosslinking. The analysis of the material revealed an increase in the gel fraction and a significant reduction in swelling of the nanocomposite material that was crosslinked with both glutaraldehyde and ionizing radiation. The radiation crosslinked nanocomposites demonstrated approximately a 90% gelation over a range of 50–300 kGy irradiation doses. The scanning electron microscopy (SEM analysis showed a homogeneous distribution of nanocomposites in the composite matrix. The thermal properties of radiation crosslinked (PVA/CEA and (PVA-CEA-nano-fillers were investigated by a thermogravimetric analysis (TGA. The mechanical properties were examined via dynamic mechanical analysis (DMA which showed significant variation because of the addition of nanocomposites. This radiation crosslinked materials show good shape memory behavior that may be useful in many applications based on the range of temperatures at which Tan δ appears.

Microstructure and Mechanical Properties of Heterogeneous Ceramic-Polymer Composite Using Interpenetrating Network

International Nuclear Information System (INIS)

Eun-Hee, K.; Yeon-Gil, J.; Chang-Yong, J.

2012-01-01

Prepolymer, which can be polymerized by a photo, has been infiltrated into a porous ceramic to improve the addition effect of polymer into the ceramic, as a function of the functionality of prepolymer. It induces the increase in the mechanical properties of the ceramic. The porous alumina (Al 2 O 3 ) and the polyurethane acrylate (PUA) with a network structure by photo-polymerization were used as the matrix and infiltration materials, respectively. The porous Al 2 O 3 matrix without the polymer shows lower values in fracture strength than the composites, since the stress is transmitted more quickly via propagation of cracks from intrinsic defects in the porous matrix. However, in the case of composites, the distribution of stress between hetero phases results in the improved mechanical properties. In addition, the mechanical properties of composites, such as elastic modulus and fracture strength, are enhanced with increasing the functionality of prepolymer attributed to the crosslinking density of polymer.

Polymer and Water Dynamics in Poly(vinyl alcohol/Poly(methacrylate Networks. A Molecular Dynamics Simulation and Incoherent Neutron Scattering Investigation

Directory of Open Access Journals (Sweden)

Ester Chiessi

2011-10-01

Full Text Available Chemically cross-linked polymer networks of poly(vinyl alcohol/poly(methacrylate form monolitic hydrogels and microgels suitable for biomedical applications, such as in situ tissue replacement and drug delivery. In this work, molecular dynamics (MD simulation and incoherent neutron scattering methods are used to study the local polymer dynamics and the polymer induced modification of water properties in poly(vinyl alcohol/poly(methacrylate hydrogels. This information is particularly relevant when the diffusion of metabolites and drugs is a requirement for the polymer microgel functionality. MD simulations of an atomic detailed model of the junction domain at the experimental hydration degree were carried out at 283, 293 and 313 K. The polymer-water interaction, the polymer connectivity and the water dynamics were investigated as a function of temperature. Simulation results are compared with findings of elastic and quasi-elastic incoherent neutron scattering measurements, experimental approaches which sample the same space-time window of MD simulations. This combined analysis shows a supercooled water component and an increase of hydrophilicity and mobility with temperature of these amphiphilic polymer networks.

Fabrication of circular microfluidic network in enzymatically-crosslinked gelatin hydrogel

Energy Technology Data Exchange (ETDEWEB)

He, Jiankang, E-mail: jiankanghe@mail.xjtu.edu.cn; Chen, Ruomeng; Lu, Yongjie; Zhan, Li; Liu, Yaxiong; Li, Dichen; Jin, Zhongmin

2016-02-01

It is a huge challenge to engineer vascular networks in vital organ tissue engineering. Although the incorporation of artificial microfluidic network into thick tissue-engineered constructs has shown great promise, most of the existing microfluidic strategies are limited to generate rectangle cross-sectional channels rather than circular vessels in soft hydrogels. Here we present a facile approach to fabricate branched microfluidic network with circular cross-sections in gelatin hydrogels by combining micromolding and enzymatically-crosslinking mechanism. Partially crosslinked hydrogel slides with predefined semi-circular channels were molded, assembled and in situ fully crosslinked to form a seamless and circular microfluidic network. The bonding strength of the resultant gelatin hydrogels was investigated. The morphology and the dimension of the resultant circular channels were characterized using scanning electron microscopy (SEM) and micro-computerized tomography (μCT). Computational fluid dynamic simulation shows that the fabrication error had little effect on the distribution of flow field but affected the maximum velocity in comparison with designed models. The microfluidic gelatin hydrogel facilitates the attachment and spreading of human umbilical endothelial cells (HUVECs) to form a uniform endothelialized layer around the circular channel surface, which successfully exhibited barrier functions. The presented method might provide a simple way to fabricate circular microfluidic networks in biologically-relevant hydrogels to advance various applications of in vitro tissue models, organ-on-a-chip systems and tissue engineering. - Highlights: • A facile method was proposed to build a circular fluidic network in gelatin hydrogel. • The fluidic network is mechanically robust and supports physiological flow. • HUVECs formed endothelialized layer around the channel to express barrier function.

Chemical cross-linking of polypropylenes towards new shape memory polymers.

Science.gov (United States)

Raidt, Thomas; Hoeher, Robin; Katzenberg, Frank; Tiller, Joerg C

2015-04-01

In this work, syndiotactic polypropylene (sPP) as well as isotactic polypropylene (iPP) are cross-linked to gain a shape memory effect. Both prepared PP networks exhibit maximum strains of 700%, stored strains of up to 680%, and recoveries of nearly 100%. While x-iPP is stable for many cycles, x-sPP ruptures after the first shape-memory cycle. It is shown by wide-angle X-ray scattering (WAXS) experiments that cross-linked iPP exhibits homoepitaxy in the temporary, stretched shape but in contrast to previous reports it contains a higher amount of daughter than mother crystals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of Supercritical CO 2 Conditioning on Cross-Linked Polyimide Membranes

KAUST Repository

Kratochvil, Adam M.

2010-05-25

The effects of supercritical CO2 (scCO2) conditioning on high-performance cross-linked polyimide membranes is examined through gas permeation and sorption experiments. Under supercritical conditions, the cross-linked polymers do not exhibit a structural reorganization of the polymer matrix that was observed in the non-cross-linkable, free acid polymer. Pure gas permeation isotherms and mixed gas permeabilities and selectivities show the cross-linked polymers to be much more stable to scCO2 conditioning than the free acid polymer. In fact, following scCO2 conditioning, the mixed gas CO2 permeabilities of the cross-linked polymers increased while the CO2/CH4 separation factors remained relatively unchanged. This response highlights the stability and high performance of these cross-linked membranes in aggressive environments. In addition, this response reveals the potential for the preconditioning of cross-linked polymer membranes to enhance productivity without sacrificing efficiency in practical applications which, in effect, provides another tool to \\'tune\\' membrane properties for a given separation. Finally, the dual mode model accurately describes the sorption and dilation characteristics of the cross-linked polymers. The changes in the dual mode sorption model parameters before and after the scCO2 exposure also provide insights into the alterations in the different glassy samples due to the cross-linking and scCO2 exposure. © 2010 American Chemical Society.

Polymeric redox-responsive delivery systems bearing ammonium salts cross-linked via disulfides

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Christian Dollendorf

2013-08-01

Full Text Available A redox-responsive polycationic system was synthesized via copolymerization of N,N-diethylacrylamide (DEAAm and 2-(dimethylaminoethyl methacrylate (DMAEMA. N,N’-bis(4-chlorobutanoylcystamine was used as disulfide-containing cross-linker to form networks by the quaternization of tertiary amine groups. The insoluble cationic hydrogels become soluble by reduction of disulfide to mercaptanes by use of dithiothreitol (DTT, tris(2-carboxyethylphosphine (TCEP or cysteamine, respectively. The soluble polymeric system can be cross-linked again by using oxygen or hydrogen peroxide under basic conditions. The redox-responsive polymer networks can be used for molecular inclusion and controlled release. As an example, phenolphthalein, methylene blue and reactive orange 16 were included into the network. After treatment with DTT a release of the dye could be recognized. Physical properties of the cross-linked materials, e.g., glass transition temperature (Tg, swelling behavior and cloud points (Tc were investigated. Redox-responsive behavior was further analyzed by rheological measurements.

Crosslinked ionic polysaccharides for stimuli-sensitive drug delivery.

Science.gov (United States)

Alvarez-Lorenzo, Carmen; Blanco-Fernandez, Barbara; Puga, Ana M; Concheiro, Angel

2013-08-01

Polysaccharides are gaining increasing attention as components of stimuli-responsive drug delivery systems, particularly since they can be obtained in a well characterized and reproducible way from the natural sources. Ionic polysaccharides can be readily crosslinked to render hydrogel networks sensitive to a variety of internal and external variables, and thus suitable for switching drug release on-off through diverse mechanisms. Hybrids, composites and grafted polymers can reinforce the responsiveness and widen the range of stimuli to which polysaccharide-based systems can respond. This review analyzes the state of the art of crosslinked ionic polysaccharides as components of delivery systems that can regulate drug release as a function of changes in pH, ion nature and concentration, electric and magnetic field intensity, light wavelength, temperature, redox potential, and certain molecules (enzymes, illness markers, and so on). Examples of specific applications are provided. The information compiled demonstrates that crosslinked networks of ionic polysaccharides are suitable building blocks for developing advanced externally activated and feed-back modulated drug delivery systems. Copyright © 2013 Elsevier B.V. All rights reserved.

Highly efficient inverted polymer solar cells based on a cross-linkable water-/alcohol-soluble conjugated polymer interlayer.

Science.gov (United States)

Zhang, Kai; Zhong, Chengmei; Liu, Shengjian; Mu, Cheng; Li, Zhengke; Yan, He; Huang, Fei; Cao, Yong

2014-07-09

A cross-linkable water/alcohol soluble conjugated polymer (WSCP) material poly[9,9-bis(6'-(N,N-diethylamino)propyl)-fluorene-alt-9,9-bis(3-ethyl(oxetane-3-ethyloxy)-hexyl) fluorene] (PFN-OX) was designed. The cross-linkable nature of PFN-OX is good for fabricating inverted polymer solar cells (PSCs) with well-defined interface and investigating the detailed working mechanism of high-efficiency inverted PSCs based on poly[4,8-bis(2-ethylhexyloxyl)benzo[1,2-b:4,5-b']dithio-phene-2,6-diyl-alt-ethylhexyl-3-fluorothithieno[3,4-b]thiophene-2-carboxylate-4,6-diyl] (PTB7) and (6,6)-phenyl-C71-butyric acid methyl ester (PC71BM) blend active layer. The detailed working mechanism of WSCP materials in high-efficiency PSCs were studied and can be summarized into the following three effects: a) PFN-OX tunes cathode work function to enhance open-circuit voltage (Voc); b) PFN-OX dopes PC71BM at interface to facilitate electron extraction; and c) PFN-OX extracts electrons and blocks holes to enhance fill factor (FF). On the basis of this understanding, the hole-blocking function of the PFN-OX interlayer was further improved with addition of a ZnO layer between ITO and PFN-OX, which led to inverted PSCs with a power conversion efficiency of 9.28% and fill factor high up to 74.4%.

Semi-Degradable Poly(β-amino ester) Networks with Temporally-Controlled Enhancement of Mechanical Properties

Science.gov (United States)

Safranski, David L.; Weiss, Daiana; Clark, J. Brian; Taylor, W.R.; Gall, Ken

2014-01-01

Biodegradable polymers are clinically used in numerous biomedical applications, and classically show a loss in mechanical properties within weeks of implantation. This work demonstrates a new class of semi-degradable polymers that show an increase in mechanical properties through degradation via a controlled shift in a thermal transition. Semi-degradable polymer networks, poly(β-amino ester)-co-methyl methacrylate, were formed from a low glass transition temperature crosslinker, poly(β-amino ester), and high glass transition temperature monomer, methyl methacrylate, which degraded in a manner dependent upon the crosslinker chemical structure. In vitro and in vivo degradation revealed changes in mechanical behavior due to the degradation of the crosslinker from the polymer network. This novel polymer system demonstrates a strategy to temporally control the mechanical behavior of polymers and to enhance the initial performance of smart biomedical devices. PMID:24769113

Revealing the Supramolecular Nature of Side-Chain Terpyridine-Functionalized Polymer Networks

Directory of Open Access Journals (Sweden)

Jérémy Brassinne

2015-01-01

Full Text Available Nowadays, finely controlling the mechanical properties of polymeric materials is possible by incorporating supramolecular motifs into their architecture. In this context, the synthesis of a side-chain terpyridine-functionalized poly(2-(dimethylaminoethyl methacrylate is reported via reversible addition-fragmentation chain transfer polymerization. By addition of transition metal ions, concentrated aqueous solutions of this polymer turn into metallo-supramolecular hydrogels whose dynamic mechanical properties are investigated by rotational rheometry. Hence, the possibility for the material to relax mechanical constrains via dissociation of transient cross-links is brought into light. In addition, the complex phenomena occurring under large oscillatory shear are interpreted in the context of transient networks.

Polymers and Cross-Linking: A CORE Experiment to Help Students Think on the Submicroscopic Level

Science.gov (United States)

Bruce, Mitchell R. M.; Bruce, Alice E.; Avargil, Shirly; Amar, Francois G.; Wemyss, Thomas M.; Flood, Virginia J.

2016-01-01

The Polymers and Cross-Linking experiment is presented via a new three phase learning cycle: CORE (Chemical Observations, Representations, Experimentation), which is designed to model productive chemical inquiry and to promote a deeper understanding about the chemistry operating at the submicroscopic level. The experiment is built on two familiar…

Characterization of nanocellulose reinforced semi-interpenetrating polymer network of poly(vinyl alcohol) & polyacrylamide composite films.

Science.gov (United States)

Mandal, Arup; Chakrabarty, Debabrata

2015-12-10

Semi-interpenetrating polymer network (semi-IPN) of poly(vinyl alcohol)/polyacrylamide was reinforced with various doses of nanocellulose. The different composite films thus prepared were characterized with respect to their mechanical, thermal, morphological and barrier properties. The composite film containing 5 wt.% of nanocellulose showed the highest tensile strength. The semi-interpenetrating polymer network of poly(vinyl alcohol)/polyacrylamide; and its various composites with nanocellulose were almost identical in their thermal stability. Each of the composites however exhibited much superior stability with respect to the linear poly(vinyl alcohol) and crosslinked polyacrylamide. The scanning electron microscopy (SEM) and atomic force microscopy (AFM) studies exhibited phase separated morphology where agglomerates of nanocellulose were found to be dispersed in the matrix of the semi-IPN. The moisture vapor transmission rate (MVTR) was the lowest for the film containing 5 wt.% of nanocellulose. Copyright © 2015 Elsevier Ltd. All rights reserved.

Segmental dynamics in poly(methyl acrylate)-poly(methyl methacrylate) sequential interpenetrating polymer networks: structural relaxation experiments

International Nuclear Information System (INIS)

Ribelles, J L Gomez; Duenas, J M Meseguer; Cabanilles, C Torregrosa; Pradas, M Monleon

2003-01-01

The miscibility of poly(methyl acrylate)-poly(methyl methacrylate) sequential interpenetrating polymer networks (IPNs) has been studied by probing the conformational mobility of the component polymer chains. These IPNs exhibit the phenomenon of forced compatibilization. In a conventional heating differential scanning calorimetry (DSC) thermogram, the highly cross-linked IPN shows a single glass transition which covers a temperature interval of around 100 d eg C; in contrast, loosely cross-linked IPNs show two glass transitions. The conformational mobility in these IPNs is studied by subjecting them to isothermal annealings at temperatures in the region of the glass transition and below it. The DSC scans measured after these treatments allow one to determine the temperature interval in which the sample is out of thermodynamic equilibrium but keeps enough conformational mobility to relax during the isothermal annealing in such a way that the enthalpy loss is measurable with the sensitivity of a conventional DSC. The results allow one to reach some conclusions about the compositional distribution of the IPN on the nanometre scale

Semi-degradable poly(β-amino ester) networks with temporally controlled enhancement of mechanical properties.

Science.gov (United States)

Safranski, David L; Weiss, Daiana; Clark, J Brian; Taylor, W Robert; Gall, Ken

2014-08-01

Biodegradable polymers are clinically used in numerous biomedical applications, and classically show a loss of mechanical properties within weeks of implantation. This work demonstrates a new class of semi-degradable polymers that show an increase in mechanical properties through degradation via a controlled shift in a thermal transition. Semi-degradable polymer networks, poly(β-amino ester)-co-methyl methacrylate, were formed from a low glass transition temperature crosslinker, poly(β-amino ester), and high glass transition temperature monomer, methyl methacrylate, which degraded in a manner dependent upon the crosslinker chemical structure. In vitro and in vivo degradation revealed changes in mechanical behavior due to the degradation of the crosslinker from the polymer network. This novel polymer system demonstrates a strategy to temporally control the mechanical behavior of polymers and to enhance the initial performance of smart biomedical devices. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Ion beam application for improved polymer surface properties

International Nuclear Information System (INIS)

Lee, E.H.; Rao, G.R.; Lewis, M.B.; Mansur, L.K.

1992-01-01

Various polymeric materials were subjected to bombardment by different energetic ions with energies ranging from 200 to 1000 keV. Tests showed substantial improvements in hardness, wear resistance, oxidation resistance, resistance to chemicals, and electrical conductivity. The magnitude of property changes was strongly dependent upon ion species, energy, dose, and polymer structure. Both hardness and electrical conductivity increased with ion energy and dose. These properties were apparently related to the effectiveness of cross-linking. Ion species with a large electronic stopping cross-section are expected to produce more crosslinking. It is believed that the polymer property improvements are commensurate with the extent of crosslinking, which is responsible for the formation of three-dimensionally-connected, carbon-rich, rigid networks. 22 refs, 5 figs

Separator Membrane from Crosslinked Poly(Vinyl Alcohol and Poly(Methyl Vinyl Ether-alt-Maleic Anhydride

Directory of Open Access Journals (Sweden)

Charu Vashisth Rohatgi

2015-03-01

Full Text Available In this work, we report separator membranes from crosslinking of two polymers, such as poly vinyl alcohol (PVA with an ionic polymer poly(methyl vinyl ether-alt-maleic anhydride (PMVE-MA. Such interpolymer-networked systems were extensively used for biomedical and desalination applications but they were not examined for their potential use as membranes or separators for batteries. Therefore, the chemical interactions between these two polymers and the influence of such crosslinking on physicochemical properties of the membrane are systematically investigated through rheology and by critical gel point study. The hydrogen bonding and the chemical interaction between PMVE-MA and PVA resulted in highly cross-linked membranes. Effect of the molecular weight of PVA on the membrane properties was also examined. The developed membranes were extensively characterized by studying their physicochemical properties (water uptake, swelling ratio, and conductivity, thermal and electrochemical properties using differential scanning calorimetry (DSC, dynamic mechanical analysis (DMA, thermo-gravimetric analysis (TGA and electrochemical impedance spectroscopy (EIS. The DSC study shows the presence of a single Tg in the membranes indicating compatibility of the two polymers in flexible and transparent films. The membranes show good stability and ion conductivity suitable for separator applications.

Separator Membrane from Crosslinked Poly(Vinyl Alcohol) and Poly(Methyl Vinyl Ether-alt-Maleic Anhydride)

Science.gov (United States)

Rohatgi, Charu Vashisth; Dutta, Naba K.; Choudhury, Namita Roy

2015-01-01

In this work, we report separator membranes from crosslinking of two polymers, such as poly vinyl alcohol (PVA) with an ionic polymer poly(methyl vinyl ether-alt-maleic anhydride) (PMVE-MA). Such interpolymer-networked systems were extensively used for biomedical and desalination applications but they were not examined for their potential use as membranes or separators for batteries. Therefore, the chemical interactions between these two polymers and the influence of such crosslinking on physicochemical properties of the membrane are systematically investigated through rheology and by critical gel point study. The hydrogen bonding and the chemical interaction between PMVE-MA and PVA resulted in highly cross-linked membranes. Effect of the molecular weight of PVA on the membrane properties was also examined. The developed membranes were extensively characterized by studying their physicochemical properties (water uptake, swelling ratio, and conductivity), thermal and electrochemical properties using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermo-gravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS). The DSC study shows the presence of a single Tg in the membranes indicating compatibility of the two polymers in flexible and transparent films. The membranes show good stability and ion conductivity suitable for separator applications. PMID:28347019

Biodegradation study of enzymatically catalyzed interpenetrating polymer network: Evaluation of agrochemical release and impact on soil fertility

Directory of Open Access Journals (Sweden)

Saruchi

2016-03-01

Full Text Available A novel interpenetrating polymer network (IPN has been synthesized through enzymatic initiation using lipase as initiator, glutaraldehyde as cross-linker, acrylic acid as primary monomer and acrylamide as secondary monomer. Biodegradability of synthesized interpenetrating polymer network was studied through soil burial and composting methods. Synthesized hydrogel was completely degraded within 70 days using composting method, while it was 86.03% degraded within 77 days using soil burial method. This was confirmed by Fourier transform Infrared spectroscopy (FTIR and Scanning electron microscopy (SEM techniques. Synthesized interpenetrating polymer network hydrogel was used as a device for controlled release of urea and also act as water releasing device. Their impact on soil fertility and plant growth was also studied. The initial diffusion coefficient has a greater value than the later diffusion coefficient indicating a higher fertilizer release rate during the early stage. Fertilizer release kinetic was also studied which showed Non-Fickian diffusion behavior, as the rate of fertilizer release was comparable to the relaxation time of the synthesized matrix. Synthesized IPN enhance the water uptake capacity up to 6.2% and 7.2% in sandy loam and clay soil, respectively.

Experimental design of mixture applied to study PVP hydrogels properties crosslinked by ionizing radiation

Energy Technology Data Exchange (ETDEWEB)

Alcantara, Mara Tania S.; Lugao, Ademar B., E-mail: maratalcantara@uol.com.b [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Taqueda, Maria Elena S. [Universidade de Sao Paulo (USP), SP (Brazil). Escola Politecnica. Dept. de Engenharia Quimica

2009-07-01

Hydrogels are three dimensional hydrophilic crosslinked polymeric networks that have capacity to swell by absorbing water or biological fluids without dissolve. Hydrogels have been widely used in different application fields from agriculture, industry and in biomedicine. The properties of a hydrogel are extremely important in selecting which materials are suitable for a specific application. So mixtures can offer hydrogels with different properties to different applications. The PVP hydrogels were prepared by gamma radiation of an aqueous polymer solution and crosslinked by gamma ray, an effective and simple method for hydrogel formation that offers some advantages over the other techniques. In this work, a mixture experimental design was used to study the relationship between polymer cross-linking and swelling properties of PVP hydrogels with PEG as plasticizer and agar as gellifier. The gel fraction was measured for every mixture specified for the experiment D-optimal designs. (author)

Experimental design of mixture applied to study PVP hydrogels properties crosslinked by ionizing radiation

International Nuclear Information System (INIS)

Alcantara, Mara Tania S.; Lugao, Ademar B.; Taqueda, Maria Elena S.

2009-01-01

Hydrogels are three dimensional hydrophilic crosslinked polymeric networks that have capacity to swell by absorbing water or biological fluids without dissolve. Hydrogels have been widely used in different application fields from agriculture, industry and in biomedicine. The properties of a hydrogel are extremely important in selecting which materials are suitable for a specific application. So mixtures can offer hydrogels with different properties to different applications. The PVP hydrogels were prepared by gamma radiation of an aqueous polymer solution and crosslinked by gamma ray, an effective and simple method for hydrogel formation that offers some advantages over the other techniques. In this work, a mixture experimental design was used to study the relationship between polymer cross-linking and swelling properties of PVP hydrogels with PEG as plasticizer and agar as gellifier. The gel fraction was measured for every mixture specified for the experiment D-optimal designs. (author)

Effect of degree of crosslinking and polymerization of 3D printable polymer/ionic liquid composites on performance of stretchable piezoresistive sensors

Science.gov (United States)

Lee, Jeongwoo; Faruk Emon, Md Omar; Vatani, Morteza; Choi, Jae-Won

2017-03-01

Ionic liquid (IL)/polymer composites (1-ethyl-3-methyl-imidazolium tetrafluoroborate (EMIMBF4)/2-[[(butylamino)carbonyl]oxy]ethyl acrylate (BACOEA)) were fabricated to use as sensing materials for stretchable piezoresistive tactile sensors. The detectability of the IL/polymer composites was enhanced because the ionic transport properties of EMIMBF4 in the composites were improved by the synergic actions between the coordinate sites generated by the local motion of BACOEA chain segments under enough activation energy. The performance of the piezoresistive sensors was investigated with the degree of crosslinking and polymerization of the IL/polymer composites. As the compressive strain was increased, the distance between two electrodes decreased, and the motion of polymer chains and IL occurred, resulting in a decrease in the electrical resistance of the sensors. We have confirmed that the sensitivity of the sensors are affected by the degree of crosslink and polymerization of the IL/polymer composites. In addition, all of the materials (skins, sensing material, and electrode) used in this study are photo-curable, and thus the stretchable piezoresistive tactile sensors can be successfully fabricated by 3D printing.

Crosslinked poly(vinyl alcohol hydrogels for wound dressing applications: A review of remarkably blended polymers

Directory of Open Access Journals (Sweden)

Elbadawy A. Kamoun

2015-01-01

Full Text Available A series of excellent poly(vinyl alcohol (PVA/polymers blend hydrogel were reviewed using different crosslinking types to obtain proper polymeric dressing materials, which have satisfied biocompatibility and sufficient mechanical properties. The importance of biodegradable–biocompatible synthetic polymers such as PVA, natural polymers such as alginate, starch, and chitosan or their derivatives has grown significantly over the last two decades due to their renewable and desirable biological properties. The properties of these polymers for pharmaceutical and biomedical application needs have attracted much attention. Thus, a considered proportion of the population need those polymeric medical applications for drug delivery, wound dressing, artificial cartilage materials, and other medical purposes, where the pressure on alternative polymeric devices in all countries became substantial. The review explores different polymers which have been blended previously in the literature with PVA as wound dressing blended with other polymeric materials, showing the feasibility, property change, and purpose which are behind the blending process with PVA.

Two Players Make a Formidable Combination: In Situ Generated Poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) Cross-Linking Gel Polymer Electrolyte toward 5 V High-Voltage Batteries.

Science.gov (United States)

Ma, Yue; Ma, Jun; Chai, Jingchao; Liu, Zhihong; Ding, Guoliang; Xu, Gaojie; Liu, Haisheng; Chen, Bingbing; Zhou, Xinhong; Cui, Guanglei; Chen, Liquan

2017-11-29

Electrochemical performance of high-voltage lithium batteries with high energy density is limited because of the electrolyte instability and the electrode/electrolyte interfacial reactivity. Hence, a cross-linking polymer network of poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) (PAMM)-based electrolyte was introduced via in situ polymerization inspired by "shuangjian hebi", which is a statement in a traditional Chinese Kungfu story similar to the synergetic effect of 1 + 1 > 2. A poly(acrylic anhydride) and poly(methyl methacrylate)-based system is very promising as electrolyte materials for lithium-ion batteries, in which the anhydride and acrylate groups can provide high voltage resistance and fast ionic conductivity, respectively. As a result, the cross-linking PAMM-based electrolyte possesses a significant comprehensive enhancement, including electrochemical stability window exceeding 5 V vs Li + /Li, an ionic conductivity of 6.79 × 10 -4 S cm -1 at room temperature, high mechanical strength (27.5 MPa), good flame resistance, and excellent interface compatibility with Li metal. It is also demonstrated that this gel polymer electrolyte suppresses the negative effect resulting from dissolution of Mn 2+ ions at 25 and 55 °C. Thus, the LiNi 0.5 Mn 1.5 O 4 /Li and LiNi 0.5 Mn 1.5 O 4 /Li 4 Ti 5 O 12 cells using the optimized in situ polymerized cross-linking PAMM-based gel polymer electrolyte deliver stable charging/discharging profiles and excellent rate performance at room temperature and even at 55 °C. These findings suggest that the cross-linking PAMM is an intriguing candidate for 5 V class high-voltage gel polymer electrolyte toward high-energy lithium-on batteries.

Radiation-crosslinking of shape memory polymers based on poly(vinyl alcohol) in the presence of carbon nanotubes

Science.gov (United States)

Basfar, A. A.; Lotfy, S.

2015-01-01

Shape memory polymers based on poly(vinyl alcohol) (SM-PVA) in the presence of 2-carboxyethyl acrylate oligomers (CEA) and multi-wall carbon nanotubes (MWCNTs) crosslinked by ionizing radiation were investigated. Chemical-crosslinking of PVA by glutaraldehyde in the presence of CEA and MWCNTs was also studied. The swelling and gel fraction of the radiation-crosslinked SM-PVA and chemically crosslinked systems were evaluated. Analysis of the swelling and gel fraction revealed a significant reduction in swelling and an increase in the gel fraction of the material that was chemically crosslinked with glutaraldehyde. The radiation-crosslinked SM-PVA demonstrated 100% gelation at an irradiation dose of 50 kGy. In addition, radiation-crosslinked SM-PVA exhibited good temperature responsive shape-memory behavior. A scanning electron microscopy (SEM) analysis was performed. The thermal properties of radiation-crosslinked SM-PVA were investigated by a thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA). The ability of the material to return or store energy (E‧), to its ability to lose energy (E″), and the ratio of these effects (Tanδ), which is called damping were examined via DMA. The temperature of Tanδ in the radiation-crosslinked SM-PVA decreased significantly by 6 and 13 °C as a result of the addition of MWCNTs. In addition, the temperature of Tanδ for SM-PVA increased as the irradiation dose increased. These radiation-crosslinked SM-PVA materials show promising shape-memory behavior based on the range of temperatures at which Tanδ appears.

Phase equilibria and phase structures of polymer blends

International Nuclear Information System (INIS)

Chalykh, Anatolii E; Gerasimov, Vladimir K

2004-01-01

Experimental, methodical and theoretical studies dealing with phase equilibria and phase structures of polymer blends are generalised. The general and specific features of the change in solubility of polymers with changes in the molecular mass and copolymer composition and upon the formation of three-dimensional cross-linked networks are described. The results of the effect of the prehistory on the phase structure and the non-equilibrium state of polymer blends are considered in detail.

A comparison of thiolated and disulfide-crosslinked polyethylenimine for nonviral gene delivery.

Science.gov (United States)

Aravindan, Latha; Bicknell, Katrina A; Brooks, Gavin; Khutoryanskiy, Vitaliy V; Williams, Adrian C

2013-09-01

Branched polyethylenimine (25 kDa) is thiolated and compared with redox-sensitive crosslinked derivatives. Both polymers thiol contents are assessed; the thiolated polymers have 390-2300 mmol SH groups/mol, whereas the crosslinked polymers have lower thiol contents. Cytotoxicity assays show that both modified polymers give lower hemolysis than unmodified PEI. Increased thiol content increases gene transfer efficiency but also elevates cytotoxicity. Crosslinking improves plasmid DNA condensation and enhances transfection efficiency, but extensive crosslinking overstabilizes the polyplexes and decreases transfection, emphasizing the need to balance polyplex stabilization and unpacking. Thus, at low levels of crosslinking, 25 kDa PEI can be an efficient redox-sensitive carrier system. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Semi-Interpenetrating Polymer Networks with Predefined Architecture for Metal Ion Fluorescence Monitoring

Directory of Open Access Journals (Sweden)

Kyriakos Christodoulou

2016-11-01

Full Text Available The development of new synthetic approaches for the preparation of efficient 3D luminescent chemosensors for transition metal ions receives considerable attention nowadays, owing to the key role of the latter as elements in biological systems and their harmful environmental effects when present in aquatic media. In this work, we describe an easy and versatile synthetic methodology that leads to the generation of nonconjugated 3D luminescent semi-interpenetrating amphiphilic networks (semi-IPN with structure-defined characteristics. More precisely, the synthesis involves the encapsulation of well-defined poly(9-anthrylmethyl methacrylate (pAnMMA (hydrophobic, luminescent linear polymer chains within a covalent poly(2-(dimethylaminoethyl methacrylate (pDMAEMA hydrophilic polymer network, derived via the 1,2-bis-(2-iodoethoxyethane (BIEE-induced crosslinking process of well-defined pDMAEMA linear chains. Characterization of their fluorescence properties demonstrated that these materials act as strong blue emitters when exposed to UV irradiation. This, combined with the presence of the metal-binding tertiary amino functionalities of the pDMAEMA segments, allowed for their applicability as sorbents and fluorescence chemosensors for transition metal ions (Fe3+, Cu2+ in solution via a chelation-enhanced fluorescence-quenching effect promoted within the semi-IPN network architecture. Ethylenediaminetetraacetic acid (EDTA-induced metal ion desorption and thus material recyclability has been also demonstrated.

An improved correlation to predict molecular weight between crosslinks based on equilibrium degree of swelling of hydrogel networks.

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Jimenez-Vergara, Andrea C; Lewis, John; Hahn, Mariah S; Munoz-Pinto, Dany J

2018-04-01

Accurate characterization of hydrogel diffusional properties is of substantial importance for a range of biotechnological applications. The diffusional capacity of hydrogels has commonly been estimated using the average molecular weight between crosslinks (M c ), which is calculated based on the equilibrium degree of swelling. However, the existing correlation linking M c and equilibrium swelling fails to accurately reflect the diffusional properties of highly crosslinked hydrogel networks. Also, as demonstrated herein, the current model fails to accurately predict the diffusional properties of hydrogels when polymer concentration and molecular weight are varied simultaneously. To address these limitations, we evaluated the diffusional properties of 48 distinct hydrogel formulations using two different photoinitiator systems, employing molecular size exclusion as an alternative methodology to calculate average hydrogel mesh size. The resulting data were then utilized to develop a revised correlation between M c and hydrogel equilibrium swelling that substantially reduces the limitations associated with the current correlation. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1339-1348, 2018. © 2017 Wiley Periodicals, Inc.

Dually cross-linked single network poly(acrylic acid) hydrogels with superior mechanical properties and water absorbency.

Science.gov (United States)

Zhong, Ming; Liu, Yi-Tao; Liu, Xiao-Ying; Shi, Fu-Kuan; Zhang, Li-Qin; Zhu, Mei-Fang; Xie, Xu-Ming

2016-06-28

Poly(acrylic acid) (PAA) hydrogels with superior mechanical properties, based on a single network structure with dual cross-linking, are prepared by one-pot free radical polymerization. The network structure of the PAA hydrogels is composed of dual cross-linking: a dynamic and reversible ionic cross-linking among the PAA chains enabled by Fe(3+) ions, and a sparse covalent cross-linking enabled by a covalent cross-linker (Bis). Under deformation, the covalently cross-linked PAA chains remain intact to maintain their original configuration, while the Fe(3+)-enabled ionic cross-linking among the PAA chains is broken to dissipate energy and then recombined. It is found that the mechanical properties of the PAA hydrogels are significantly influenced by the contents of covalent cross-linkers, Fe(3+) ions and water, which can be adjusted within a substantial range and thus broaden the applications of the hydrogels. Meanwhile, the PAA hydrogels have excellent recoverability based on the dynamic and reversible ionic cross-linking enabled by Fe(3+) ions. Moreover, the swelling capacity of the PAA hydrogels is as high as 1800 times in deionized water due to the synergistic effects of ionic and covalent cross-linkings. The combination of balanced mechanical properties, efficient recoverability, high swelling capacity and facile preparation provides a new method to obtain high-performance hydrogels.

A Facile and General Approach to Recoverable High-Strain Multishape Shape Memory Polymers.

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Li, Xingjian; Pan, Yi; Zheng, Zhaohui; Ding, Xiaobin

2018-03-01

Fabricating a single polymer network with no need to design complex structures to achieve an ideal combination of tunable high-strain multiple-shape memory effects and highly recoverable shape memory property is a great challenge for the real applications of advanced shape memory devices. Here, a facile and general approach to recoverable high-strain multishape shape memory polymers is presented via a random copolymerization of acrylate monomers and a chain-extended multiblock copolymer crosslinker. As-prepared shape memory networks show a large width at the half-peak height of the glass transition, far wider than current classical multishape shape memory polymers. A combination of tunable high-strain multishape memory effect and as high as 1000% recoverable strain in a single chemical-crosslinking network can be obtained. To the best of our knowledge, this is the first thermosetting material with a combination of highly recoverable strain and tunable high-strain multiple-shape memory effects. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shape-Memory Hydrogels: Evolution of Structural Principles To Enable Shape Switching of Hydrophilic Polymer Networks.

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Löwenberg, Candy; Balk, Maria; Wischke, Christian; Behl, Marc; Lendlein, Andreas

2017-04-18

The ability of hydrophilic chain segments in polymer networks to strongly interact with water allows the volumetric expansion of the material and formation of a hydrogel. When polymer chain segments undergo reversible hydration depending on environmental conditions, smart hydrogels can be realized, which are able to shrink/swell and thus alter their volume on demand. In contrast, implementing the capacity of hydrogels to switch their shape rather than volume demands more sophisticated chemical approaches and structural concepts. In this Account, the principles of hydrogel network design, incorporation of molecular switches, and hydrogel microstructures are summarized that enable a spatially directed actuation of hydrogels by a shape-memory effect (SME) without major volume alteration. The SME involves an elastic deformation (programming) of samples, which are temporarily fixed by reversible covalent or physical cross-links resulting in a temporary shape. The material can reverse to the original shape when these molecular switches are affected by application of a suitable stimulus. Hydrophobic shape-memory polymers (SMPs), which are established with complex functions including multiple or reversible shape-switching, may provide inspiration for the molecular architecture of shape-memory hydrogels (SMHs), but cannot be identically copied in the world of hydrophilic soft materials. For instance, fixation of the temporary shape requires cross-links to be formed also in an aqueous environment, which may not be realized, for example, by crystalline domains from the hydrophilic main chains as these may dissolve in presence of water. Accordingly, dual-shape hydrogels have evolved, where, for example, hydrophobic crystallizable side chains have been linked into hydrophilic polymer networks to act as temperature-sensitive temporary cross-links. By incorporating a second type of such side chains, triple-shape hydrogels can be realized. Considering the typically given light

Effects of (monomer - crosslinker – initiator) composition during non imprinted polymers synthesis for catechin retention

Science.gov (United States)

Triadhi, U.; Zulfikar, M. A.; Setiyanto, H.; Amran, M. B.

2018-05-01

MISPE (molecularly imprinted Solid Phase Extraction) is a separation technique using a solid adsorbent as a principle of MI (molecularly imprinted). Methacrylic acid (MAA) was used as a monomer, ethylene glycol dimethacrylate (EGDMA) as a crosslinker, benzoyl peroxide (BPO) as an initiator and acetonitrile (ACN) as a porogen. Catechin will be used as the template. Thermal and microwave methods were employed in the synthesis method. When analyzed using FTIR spectra, it was found that there were no significant differences between NIP (non-imprinted polymer) resulting from thermal method and that resulting from microwave method. Preparation of polymers by microwave method required 4 mins at 60-65 °C, significantly less than thermal method, that took 60 minutes at the same temperature. The variations of mole ratios of the monomer, the crosslinker, and the initiator were also performed. Based on the FTIR spectra, intensity of some peaks were changed due to the decreases of concentration. The optimum composition for NIP synthesis was MAA: EGDMA: BPO ratio of 5:30:0.5 (in mmole). The TGA curve showed that the NIP sythesized using microwave method experienced mass loss of around 98.50% at 604.8 °C.

Production of radiation crosslinked polymeric compositions using diacetylenes

International Nuclear Information System (INIS)

Patel, G.N.

1979-01-01

Crosslinked polymeric compositions, useful as electrical insulators, heat shrinkable packaging, and lightweight foam plastics, are described. The crosslinked polymeric compositions are produced by admixing a diacetylene monomer, oligomer, polymer or mixture thereof, wherein the monomer has the formula, RNHCO-O-CH 2 -C==C-C==C-CH- 2 -O-OCNHR' in which R and R' are the same or different and are alkyl containing 1 to 20 carbon atoms, with a thermoplastic crosslinkable polymer and then subjecting the resulting mixture to actinic radiation

The radiation crosslinking of ethylene copolymers

International Nuclear Information System (INIS)

Burns, N.M.

1979-01-01

The enhanced radiation crosslinking tendency of ethylene-vinyl acetate and ethylene-ethyl acrylate copolymers over ethylene homopolymer is proportional to the comonomer content. This is caused by an increase in the amorphous polymer content and by structure-related factors. The copolymers crosslink by a random process that for ethylene-vinyl acetate copolymer involves some crosslinking through the acetoxy group of the comonomer. While knowledge of the process for the crosslinking of ethylene-ethyl acrylate copolymer is less certain, it is currently believed to occur primarily at the branch point on the polymer backbone. Data relating comonomer content and the molecular weight of the copolymers to the radiation crosslinking levels realized were developed to aid in resin selection by the formulator. Triallyl cyanurate cure accelerator was found to be less effective in ethylene-vinyl acetate copolymer than in homopolymer and to have no effect on gel development in ethylene-ethyl acrylate copolymer. (author)

Porous Polystyrene Monoliths and Microparticles Prepared from Core Cross-linked Star (CCS) Polymers-Stabilized Emulsions.

Science.gov (United States)

Chen, Qijing; Shi, Ting; Han, Fei; Li, Zihan; Lin, Chao; Zhao, Peng

2017-08-17

A hydrophobic CCS polymer of poly(benzyl methacrylate) (PBzMA) was prepared in toluene by reversible addition-fragmentation chain transfer (RAFT)-mediated dispersion polymerization. The CCS polymer, with poly(benzyl methacrylate) as the arm and crosslinked N, N'-bis(acryloyl)cystamine (BAC) as the core, was confirmed by characterization with gel permeation chromatography (GPC) and nuclear magnetic resonance (NMR) spectroscopy. Three kinds of oils (toluene, anisole and styrene) were chosen to study the emulsification properties of PBzMA CCS polymer. The oils can be emulsified by CCS polymer to form water-in-oil (w/o) emulsions. Moreover, w/o high internal phase emulsions (HIPEs) can be obtained with the increase of toluene and styrene volume fractions from 75% to 80%. Porous polystyrene monolith and microparticles were prepared from the emulsion templates and characterized by the scanning electronic microscopy (SEM). With the internal phase volume fraction increased, open-pore porous monolith was obtained.

Modification of polylactide bioplastic using hyperbranched polymer based nanostructures

Science.gov (United States)

Bhardwaj, Rahul

maximum average matrix ligament thickness was 114 nm for a toughened polylactide nanoblend and correlated well with the theoretical prediction of the matrix ligament thickness. Fourier transform infrared spectroscopy and dynamic mechanical thermal analysis proved the crosslinking of the HBP phase in the PLA matrix. The crosslinked HBP was effective at hydroxyl (-OH) to anhydride molar ratios of: 2:1, 1:1 or 1:2. The glass transition temperature values of the crosslinked HBP phase at these molar ratios were observed to deviate from the predictions made by the Fox equation. The hydrophilic nature of the hyperbranched polymer was altered to hydrophobic by incorporation of polyanhydride crosslinker, as demonstrated by the increase in the contact angle with water. Rheological studies showed that there was a network formation in the PLA matrix after in-situ crosslinking of HBP. The HBP was found to reduce the melt viscosity of PLA dramatically and this effect was maintained even after its in-situ crosslinking in the PLA matrix. Finally, the current research unwraps the new opportunities provided by the unique physical and chemical properties of highly functional hyperbranched polymers in generating new nanostructured multiphase polymer systems with enhanced properties.

pH responsive cross-linked polymeric matrices based on natural polymers: effect of process variables on swelling characterization and drug delivery properties.

Science.gov (United States)

Naeem, Fahad; Khan, Samiullah; Jalil, Aamir; Ranjha, Nazar Muhammad; Riaz, Amina; Haider, Malik Salman; Sarwar, Shoaib; Saher, Fareha; Afzal, Samrin

2017-01-01

Introduction: The current work was aimed to design and synthesize novel crosslinked pH-sensitive gelatin/pectin (Ge/Pec) hydrogels using different polymeric ratios and to explore the effect of polymers and degree of crosslinking on dynamic, equilibrium swelling and in vitro release behavior of the model drug (Mannitol). Methods: The Ge/Pec based hydrogels were prepared using glutaraldehyde as the crosslinker. Various structural parameters that affect their release behavior were determined, including swelling study, porosity, sol-gel analysis, average molecular weight between crosslinks (Mc), volume fraction of polymer (V2,s), solvent interaction parameter (χ) and diffusion coefficient. The synthesized hydrogels were subjected to various characterization tools like Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and DSC differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Results: The hydrogels show highest water uptake and release at lower pH values. The FTIR spectra showed an interaction between Ge and Pec, and the drug-loaded samples also showed the drug-related peaks, indicating proper loading of the drug. DSC and TGA studies confirmed the thermal stability of hydrogel samples, while SEM showed the porous nature of hydrogels. The drug release followed non-Fickian diffusion or anomalous mechanism. Conclusion: Aforementioned characterizations reveal the successful formation of copolymer hydrogels. The pH-sensitive swelling ability and drug release behavior suggest that the rate of polymer chain relaxation and drug diffusion from these hydrogels are comparable which also predicts their possible use for site-specific drug delivery.

Conducting polymer networks synthesized by photopolymerization-induced phase separation

Science.gov (United States)

Yamashita, Yuki; Komori, Kana; Murata, Tasuku; Nakanishi, Hideyuki; Norisuye, Tomohisa; Yamao, Takeshi; Tran-Cong-Miyata, Qui

2018-03-01

Polymer mixtures composed of double networks of a polystyrene derivative (PSAF) and poly(methyl methacrylate) (PMMA) were alternatively synthesized by using ultraviolet (UV) and visible (Vis) light. The PSAF networks were generated by UV irradiation to photodimerize the anthracene (A) moieties labeled on the PSAF chains, whereas PMMA networks were produced by photopolymerization of methyl methacrylate (MMA) monomer and the cross-link reaction using ethylene glycol dimethacrylate (EGDMA) under Vis light irradiation. It was found that phase separation process of these networks can be independently induced and promptly controlled by using UV and Vis light. The characteristic length scale distribution of the resulting co-continuous morphology can be well regulated by the UV and Vis light intensity. In order to confirm and utilize the connectivity of the bicontinuous morphology observed by confocal microscopy, a very small amount, 0.1 wt%, of multi-walled carbon nanotubes (MWCNTs) was introduced into the mixture and the current-voltage (I-V) relationship was subsequently examined. Preliminary data show that MWCNTs are preferentially dispersed in the PSAF-rich continuous domains and the whole mixture became electrically conducting, confirming the connectivity of the observed bi-continuous morphology. The experimental data obtained in this study reveal a promising method to design various scaffolds for conducting soft matter taking advantages of photopolymerization-induced phase separation.

Interpenetrating Polymer Network Hydrogels Based on Gelatin and PVA by Biocompatible Approaches: Synthesis and Characterization

Directory of Open Access Journals (Sweden)

Eltjani-Eltahir Hago

2013-01-01

Full Text Available In this work, a new approach was introduced to prepare interpenetrating polymer network PVA/GE hydrogels by cross-linking of various concentration gelatin in the presence of transglutaminase enzyme by using the freezing-thawing cycles technique. The effects of freezing-thawing cycles on the properties of morphological characterization, gel fraction, swelling, mechanical, and MTT assay were investigated. The IPN PVA/GE hydrogels showed excellent physical and mechanical Properties. MTT assay data and the fibroblasts culture also showed excellent biocompatibility and good proliferation. This indicates that the IPN hydrogels are stable enough for various biomedical applications.

Influence of polymer network parameters of tragacanth gum-based pH responsive hydrogels on drug delivery.

Science.gov (United States)

Singh, Baljit; Sharma, Vikrant

2014-01-30

The present article deals with design of tragacanth gum-based pH responsive hydrogel drug delivery systems. The characterization of hydrogels has been carried out by SEMs, EDAX, FTIR, (13)C NMR, XRD, TGA/DTA/DTG and swelling studies. The correlation between reaction conditions and structural parameters of polymer networks such as polymer volume fraction in the swollen state (ϕ), Flory-Huggins interaction parameter (χ), molecular weight of the polymer chain between two neighboring cross links (M¯c), crosslink density (ρ) and mesh size (ξ) has been determined. The different kinetic models such as zero order, first order, Higuchi square root law, Korsmeyer-Peppas model and Hixson-Crowell cube root model were applied and it has been observed that release profile of amoxicillin best followed the first order model for the release of drug from the polymer matrix. The swelling of the hydrogels and release of drug from the drug loaded hydrogels occurred through non-Fickian diffusion mechanism in pH 7.4 solution. Copyright © 2013 Elsevier Ltd. All rights reserved.

Deformation and concentration fluctuations under stretching in a polymer network with free chains. The ``butterfly`` effect; Fluctuations de deformation et de concentration sous etirement dans un reseau polymere contenant des chaines libres. L`effet ``papillon``

Energy Technology Data Exchange (ETDEWEB)

Ramzi, A

1994-06-01

Small Angle Neutron Scattering gives access to concentration fluctuations of mobile labeled polymer chains embedded in a polymer network. At rest they appear progressively larger than for random mixing, with increasing ratio. Under uniaxial stretching, they decrease towards ideal mixing along the direction perpendicular to stretching, and can grow strongly along the parallel one, including the zero scattering vector q limit. This gives rise to intensity contours with double-winged patterns, in the shape of the figure `8`, or of `butterfly`. Random crosslinking and end-linking of monodisperse chains have both been studied. The strength of the `butterfly` effect increases with the molecular weight of the free chains, the crosslinking ratio, the network heterogeneity, and the elongation ratio. Eventually, the signal collapses on an `asymptotic` function I(q), of increasing correlation length with the elongation ratio. Deformation appears heterogeneous, maximal for soft areas, where the mobile chains localize preferentially. This could be due to spontaneous fluctuations, or linked to frozen fluctuations of the crosslink density. However, disagreement with the corresponding theoretical expressions makes it necessary to account for the spatial correlations of crosslink density, and their progressive unscreening as displayed by the asymptotic behavior. Networks containing pending labeled chains and free labeled stars lead to more precise understanding of the diffusion of free species and the heterogeneity of the deformation. It seems that the latter occurs even without diffusion for heterogeneous enough networks. In extreme cases (of the crosslinking parameters), the spatial correlations display on apparent fractal behavior, of dimensions 2 to 2.5, which is discussed here in terms of random clusters. 200 refs., 95 figs., 21 tabs., 10 appends.

A three-dimensional transient mixed hybrid finite element model for superabsorbent polymers with strain-dependent permeability

NARCIS (Netherlands)

Yu, Cong; Malakpoor, Kamyar; Huyghe, Jacques M.

2018-01-01

A hydrogel is a cross-linked polymer network with water as solvent. Industrially widely used superabsorbent polymers (SAP) are partially neutralized sodium polyacrylate hydrogels. The extremely large degree of swelling is one of the most distinctive characteristics of such hydrogels, as the volume

Studies on the effect of virtual crosslinking on the hydrolytic stability of novel aliphatic polyurethane ureas for blood contact applications.

Science.gov (United States)

Thomas, V; Jayabalan, M

2001-07-01

The effect of virtual crosslinking on the hydrolytic stability of completely aliphatic novel poly(urethane ureas), HFL9-PU1 (hard-segment content 57.5%) and HFL13-PU2 (hard-segment content 67.9%) based on 4,4'-methylene bis(cyclohexyl isocyanate) (H(12)MDI)-hydroxy-terminated polybutadiene-1,6-hexamethylene diamine, was studied. Fourier transform infrared-attenuated total reflectance and wide-angle X-ray diffraction studies revealed hydrogen-bonding interaction and microphase separation and formation of crystallites by short- and long-range ordering in hard-segment domains. Three-dimensional networks from hydrogen bonding in the present polymers lead to virtually crosslinking and insolubility. These polymers were noncytotoxic to L929 fibroblast cells. The hemolytic potential is below the accepted limit. The studies on in vitro biostability in Ringer's solution, phosphate buffered saline, and papain enzyme revealed no weight loss. The infrared spectral studies revealed changes in the surface, especially on HFL9-PU1 aged in Ringer's solution and phosphate buffered saline, and no changes when aged in papain. The marginal changes noticed in tensile properties were attributed to the changes in degree of hydrogen bonding and associated rearrangement of molecular structure in the bulk. The results revealed that the lesser the crosslinking in virgin polymer, the higher the crosslinking in aged polymer and vice versa. Increased crosslinking during aging provided increased tensile properties in the aged polymer over the virgin polymer and vice versa. For comparison, an aliphatic polyetherurethane urea (HFL16-PU3) was also synthesized using poly(oxy tetra methylene glycol) in addition to the above reactants. Though both HFL9-PU1 and HFL16-PU3 contained the same hard-segment content, the aged sample of the latter showed decreased tensile properties with increased crosslinking during aging in contrast to the former. This was attributed to less microphase separation in the

Polymer hydrogels as optimized delivery systems

International Nuclear Information System (INIS)

Batista, Jorge G.S.; Varca, Gustavo H.C.; Ferraz, Caroline C.; Garrido, Gabriela P.; Diniz, Bruna M.; Carvalho, Vinicius S.; Lugao, Ademar B.

2013-01-01

Hydrogels are formed by polymers capable of absorbing large quantities of water. They consist of one or more three-dimensionally structured polymer networks formed by macromolecular chains linked by covalent bonds-crosslinks - and physical interactions. The application of hydrogels, has been widely studied. Biodegradable synthetic or natural polymers such as chitosan, starch and poly-lactic-co-glycolic acid, have properties that allow the development of biodegradable systems for drug and nutraceutics delivery. This study aimed to develop polymeric hydrogels based on polyvinyl alcohol, polyacrylamide and polyvinylpyrrolidone using ionizing radiation in order to develop hydrogels for improved loading and release of compounds. Polymer solutions were solubilized in water and poured into thermoformed packages. After sealing, the material was subjected to γ-irradiation at 25kGy. The samples were assayed by means of mechanical properties, gel fraction and swelling degree. Nanostructure characterization was performed using Flory's equation to determine crosslinking density. The systems developed showed swelling degree and adequate mechanical resistance. The nanostructure evaluation showed different results for each system demonstrating the need of choosing the polymer based on the specific properties of each material. (author)

Polymer hydrogels as optimized delivery systems

Energy Technology Data Exchange (ETDEWEB)

Batista, Jorge G.S.; Varca, Gustavo H.C.; Ferraz, Caroline C.; Garrido, Gabriela P.; Diniz, Bruna M.; Carvalho, Vinicius S.; Lugao, Ademar B., E-mail: jorgegabriel@usp.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

2013-07-01

Hydrogels are formed by polymers capable of absorbing large quantities of water. They consist of one or more three-dimensionally structured polymer networks formed by macromolecular chains linked by covalent bonds-crosslinks - and physical interactions. The application of hydrogels, has been widely studied. Biodegradable synthetic or natural polymers such as chitosan, starch and poly-lactic-co-glycolic acid, have properties that allow the development of biodegradable systems for drug and nutraceutics delivery. This study aimed to develop polymeric hydrogels based on polyvinyl alcohol, polyacrylamide and polyvinylpyrrolidone using ionizing radiation in order to develop hydrogels for improved loading and release of compounds. Polymer solutions were solubilized in water and poured into thermoformed packages. After sealing, the material was subjected to γ-irradiation at 25kGy. The samples were assayed by means of mechanical properties, gel fraction and swelling degree. Nanostructure characterization was performed using Flory's equation to determine crosslinking density. The systems developed showed swelling degree and adequate mechanical resistance. The nanostructure evaluation showed different results for each system demonstrating the need of choosing the polymer based on the specific properties of each material. (author)

Controlling Hydrogel Mechanics via Bio-Inspired Polymer-Nanoparticle Bond Dynamics.

Science.gov (United States)

Li, Qiaochu; Barrett, Devin G; Messersmith, Phillip B; Holten-Andersen, Niels

2016-01-26

Interactions between polymer molecules and inorganic nanoparticles can play a dominant role in nanocomposite material mechanics, yet control of such interfacial interaction dynamics remains a significant challenge particularly in water. This study presents insights on how to engineer hydrogel material mechanics via nanoparticle interface-controlled cross-link dynamics. Inspired by the adhesive chemistry in mussel threads, we have incorporated iron oxide nanoparticles (Fe3O4 NPs) into a catechol-modified polymer network to obtain hydrogels cross-linked via reversible metal-coordination bonds at Fe3O4 NP surfaces. Unique material mechanics result from the supra-molecular cross-link structure dynamics in the gels; in contrast to the previously reported fluid-like dynamics of transient catechol-Fe(3+) cross-links, the catechol-Fe3O4 NP structures provide solid-like yet reversible hydrogel mechanics. The structurally controlled hierarchical mechanics presented here suggest how to develop hydrogels with remote-controlled self-healing dynamics.

Time-dependent deformation of polymer network in polymer-stabilized cholesteric liquid crystals (Conference Presentation)

Science.gov (United States)

Lee, Kyung Min; Tondiglia, Vincent P.; Bunning, Timothy J.; White, Timothy J.

2017-02-01

Recently, we reported direct current (DC) field controllable electro-optic (EO) responses of negative dielectric anisotropy polymer stabilized cholesteric liquid crystals (PSCLCs). A potential mechanism is: Ions in the liquid crystal mixtures are trapped in/on the polymer network during the fast photopolymerization process, and the movement of ions by the application of the DC field distorts polymer network toward the negative electrode, inducing pitch variation through the cell thickness, i.e., pitch compression on the negative electrode side and pitch expansion on positive electrode side. As the DC voltage is directly applied to a target voltage, charged polymer network is deformed and the reflection band is tuned. Interestingly, the polymer network deforms further (red shift of reflection band) with time when constantly applied DC voltage, illustrating DC field induced time dependent deformation of polymer network (creep-like behavior). This time dependent reflection band changes in PSCLCs are investigated by varying the several factors, such as type and concentration of photoinitiators, liquid crystal monomer content, and curing condition (UV intensity and curing time). In addition, simple linear viscoelastic spring-dashpot models, such as 2-parameter Kelvin and 3-parameter linear models, are used to investigate the time-dependent viscoelastic behaviors of polymer networks in PSCLC.

Self-Healing and Thermo-Responsive Dual-Crosslinked Alginate Hydrogels based on Supramolecular Inclusion Complexes

Science.gov (United States)

Miao, Tianxin; Fenn, Spencer L.; Charron, Patrick N.; Oldinski, Rachael A.

2015-01-01

β-cyclodextrin (β-CD), with a lipophilic inner cavity and hydrophilic outer surface, interacts with a large variety of non-polar guest molecules to form non-covalent inclusion complexes. Conjugation of β-CD onto biomacromolecules can form physically-crosslinked hydrogel networks upon mixing with a guest molecule. Herein describes the development and characterization of self-healing, thermo-responsive hydrogels, based on host-guest inclusion complexes between alginate-graft-β-CD and Pluronic® F108 (poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol)). The mechanics, flow characteristics, and thermal response were contingent on the polymer concentrations, and the host-guest molar ratio. Transient and reversible physical crosslinking between host and guest polymers governed self-assembly, allowing flow under shear stress, and facilitating complete recovery of the material properties within a few seconds of unloading. The mechanical properties of the dual-crosslinked, multi-stimuli responsive hydrogels were tuned as high as 30 kPa at body temperature, and are advantageous for biomedical applications such as drug delivery and cell transplantation. PMID:26509214

Synthesis of silver nanoparticles in hydrogels crosslinked by ionizing radiation

International Nuclear Information System (INIS)

Alcantara, Maria Tania S.; Oliani, Washington L.; Brant, Antonio J.C.; Oliveira, Maria Jose A. de; Riella, Humberto Gracher; Lugao, Ademar B.

2013-01-01

Hydrogel is defined as a polymeric material which exhibits the ability to swell and retain a significant fraction of water within its structure without dissolving the polymeric network. Silver nanoparticles (AgNPs) are used in a range of medicinal products based on hydrogels and diverse other products due to their antibacterial properties at low concentrations. The use of ionizing radiation in the production process of hydrogels of poly(N-vinyl-2-pyrrolidone) (PVP) and poly(vinyl alcohol) (PVA) in aqueous solutions enables the crosslinking of their polymer chains. If polymer solutions contain Ag + ions, these can be reduced radiolytically to nanocrystalline silver. The objective of this study was to investigate the reduction of Ag + ions by gamma-irradiation for the synthesis of AgNPs in hydrogels of PVA and PVP as main polymers and to make a comparison of the performance of the two polymeric matrices, chiefly focusing on the effect of the AgNPs' synthesis on the crosslinking of both polymers. The properties of the hydrogel matrices obtained were evaluated from tests of gel fraction, swelling in water, and stress-strain. The results of mechanical properties of PVA matrix were higher than those of PVP one whereas the latter exhibited a higher swelling degree. The reduction of silver ions was confirmed by UV-visible absorption spectrum, whose characteristics also indicated the formation of silver nanoparticles in both arrays. (author)

pH responsive cross-linked polymeric matrices based on natural polymers: effect of process variables on swelling characterization and drug delivery properties

Directory of Open Access Journals (Sweden)

Fahad Naeem

2017-08-01

Full Text Available Introduction: The current work was aimed to design and synthesize novel crosslinked pH-sensitive gelatin/pectin (Ge/Pec hydrogels using different polymeric ratios and to explore the effect of polymers and degree of crosslinking on dynamic, equilibrium swelling and in vitro release behavior of the model drug (Mannitol. Methods: The Ge/Pec based hydrogels were prepared using glutaraldehyde as the crosslinker. Various structural parameters that affect their release behavior were determined, including swelling study, porosity, sol-gel analysis, average molecular weight between crosslinks (Mc, volume fraction of polymer (V2,s, solvent interaction parameter (χ and diffusion coefficient. The synthesized hydrogels were subjected to various characterization tools like Fourier transform infrared spectroscopy (FTIR, X-ray diffraction (XRD and DSC differential scanning calorimetry (DSC and scanning electron microscopy (SEM. Results: The hydrogels show highest water uptake and release at lower pH values. The FTIR spectra showed an interaction between Ge and Pec, and the drug-loaded samples also showed the drug-related peaks, indicating proper loading of the drug. DSC and TGA studies confirmed the thermal stability of hydrogel samples, while SEM showed the porous nature of hydrogels. The drug release followed non-Fickian diffusion or anomalous mechanism. Conclusion: Aforementioned characterizations reveal the successful formation of copolymer hydrogels. The pH-sensitive swelling ability and drug release behavior suggest that the rate of polymer chain relaxation and drug diffusion from these hydrogels are comparable which also predicts their possible use for site-specific drug delivery.

An investigation of cell growth and detachment from thermoresponsive physically crosslinked networks.

Science.gov (United States)

Healy, Deirdre; Nash, Maria; Gorleov, Alexander; Thompson, Kerry; Dockery, Peter; Rochev, Yury

2017-11-01

The primary aim of this investigation was to determine the biocompatibility and cell culture potential of a newly designed class of thermoresponsive polymers. The attractiveness of these polymers lies in the fact that they swell rather than dissolve when the temperature is reduced below their respective lower critical solution temperature, due to the incorporation of octadecyl methacrylate (ODMA). The ODMA monomer acts as a physical crosslinker, preventing polymer dissolution upon temperature reduction. Two polymers were studied in this investigation poly(N isorpoylacrylamide (NIPAm)(99.25%)-co-ODMA(0.75%)) and poly(NIPAm(65%)-co-N-tert-butylacrylamide (NtBAm)(34.25%)-co-ODMA(0.75%)). Thin thermoresponsive films of the polymers were prepared via spin coating. 3T3 cells were then seeded on the prepared films and cell viability was assessed quantitatively through cell viability and activity assays and qualitatively by light microscopy. Cells were successfully seeded and grown on the poly(NIPAm-co-ODMA) and poly(NIPAm-co-NtBAm-co-ODMA) copolymer films after film modification with cell adhesion promoters (CAPs). Cell sheets successfully detached from the CAP coated poly(NIPAm-co-ODMA) platforms upon temperature reduction. Copyright © 2017 Elsevier B.V. All rights reserved.

Thermoresponsive Polymers for Biomedical Applications

Directory of Open Access Journals (Sweden)

Theoni K. Georgiou

2011-08-01

Full Text Available Thermoresponsive polymers are a class of “smart” materials that have the ability to respond to a change in temperature; a property that makes them useful materials in a wide range of applications and consequently attracts much scientific interest. This review focuses mainly on the studies published over the last 10 years on the synthesis and use of thermoresponsive polymers for biomedical applications including drug delivery, tissue engineering and gene delivery. A summary of the main applications is given following the different studies on thermoresponsive polymers which are categorized based on their 3-dimensional structure; hydrogels, interpenetrating networks, micelles, crosslinked micelles, polymersomes, films and particles.

In-situ Plasticized Cross-linked Polymer Composite Electrolyte Enhanced with Lithium-ion Conducting Nanofibers for Ambient All-Solid-State Lithium-ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Yan, Chaoyi; Zhu, Pei; Jia, Hao; Zhu, Jiadeng; Selvan, R. Kalai; Li, Ya; Dong, Xia; Du, Zhuang; Angunawela, Indunil; Wu, Nianqiang; Dirican, Mahmut

2018-04-29

Solid electrolytes have been gaining attention recently for the development of next-generation Li-ion batteries due to the substantial improvements in stability and safety. Among various types of solid electrolytes, composite solid electrolytes (CSEs) exhibit both high ionic conductivity and excellent interfacial contact with the electrodes. Incorporating active nanofibers into the polymer matrix demonstrates an effective method to fabricate CSEs. However, current CSEs based on traditional poly(ethylene oxide) (PEO) polymer suffer from the poor ionic conductivity of PEO and agglomeration effect of inorganic fillers at high concentrations, which limit further improvements in Li+ conductivity and electrochemical stability. Herein, we synthesize a novel PEO based cross-linked polymer (CLP) as the polymer matrix with naturally amorphous structure and high room-temperature ionic conductivity of 2.40 × 10-4 S cm-1. Li0.3La0.557TiO3 (LLTO) nanofibers incorporated composite solid electrolytes (L-CLPCSE) exhibit enhanced ionic conductivity without showing filler agglomeration. The high content of Li-conductive nanofibers improves the mechanical strength, ensures the conductive networks, and increases the total Li+ conductivity to 3.31 × 10-4 S cm-1. The all-solid-state Li|LiFePO4 batteries with L-CLPCSE are able to deliver attractive specific capacity of 147 mAh g-1 at room temperature, and no evident dendrite is found at the anode/electrolyte interface after 100 cycles.

Chemometric, physicomechanical and rheological analysis of the sol-gel dynamics and degree of crosslinking of glycosidic polymers

International Nuclear Information System (INIS)

Choonara, Y E; Pillay, V; Singh, N; Ndesendo, V M K; Khan, R A

2008-01-01

The influence of calcium (Ca 2+ ), zinc (Zn 2+ ) and barium (Ba 2+ ) ions on the sol-gel interconversion dynamics, degree of crosslinking and the matrix resilience of crosslinked alginate gelispheres was determined. The dependent compositional and operational variables of crosslinking make it a challenging task to optimize the degree of crosslinking and the physicomechanical properties of alginate gelispheres. The combinatory approach of textural profiling, assessing pertinent rheological descriptors and chemometric model analysis of the sol-gel interconversion mechanisms and energy paradigms involved during crosslinking, hydration and erosion of gelispheres was explored. Molecular structural modelling of the gelispheres provided a mechanistic understanding of the sol-gel interconversion phenomena and their influence on the degree of crosslinking, the hydrational dynamics and gelisphere formation. Rheological analysis revealed offset yield point values of 6.1 mg ml -1 and 8.0 mg ml -1 were computed from fitted regression curves for determining the crosslinker concentration required for combinatory crosslinkers such as Ca/Zn/Ba ions and Ba/Zn, respectively. The influence of hydration on the erosion was a direct function of the gelispheres physicomechanical strength. Textural profiling characterized the gelisphere matrices for their resilience. The various crosslinkers interacted with monomeric units at varying intensities. Ba-crosslinked gelispheres were brittle with dense polymeric networks. Zn-crosslinked gelispheres produced permeable resilient matrices when hydrated and Ca-crosslinked gelispheres demonstrated intermediate resilience with greater G/M ratio alginate grades. Chemometrical analysis explicated a potential link between several phenomena such as the type of crosslinkers employed, the static shear-rate viscosity attained, the matrix resilience and the associated sol-gel mechanisms and energy paradigms of crosslinked gelispheres

Statistical mechanics of polymer networks of any topology

International Nuclear Information System (INIS)

Duplantier, B.

1989-01-01

The statistical mechanics is considered of any polymer network with a prescribed topology, in dimension d, which was introduced previously. The basic direct renormalization theory of the associated continuum model is established. It has a very simple multiplicative structure in terms of the partition functions of the star polymers constituting the vertices of the network. A calculation is made to O(ε 2 ), where d = 4 -ε, of the basic critical dimensions σ L associated with any L=leg vertex (L ≥ 1). From this infinite series of critical exponents, any topology-dependent critical exponent can be derived. This is applied to the configuration exponent γ G of any network G to O(ε 2 ), including L-leg star polymers. The infinite sets of contact critical exponents θ between multiple points of polymers or between the cores of several star polymers are also deduced. As a particular case, the three exponents θ 0 , θ 1 , θ 2 calculated by des Cloizeaux by field-theoretic methods are recovered. The limiting exact logarithmic laws are derived at the upper critical dimension d = 4. The results are generalized to the series of topological exponents of polymer networks near a surface and of tricritical polymers at the Θ-point. Intersection properties of networks of random walks can be studied similarly. The above factorization theory of the partition function of any polymer network over its constituting L-vertices also applies to two dimensions, where it can be related to conformal invariance. The basic critical exponents σ L and thus any topological polymer exponents are then exactly known. Principal results published elsewhere are recalled

Ion conducting polymers and polymer blends for alkali metal ion batteries

Science.gov (United States)

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

Network approach towards understanding the crazing in glassy amorphous polymers

Science.gov (United States)

Venkatesan, Sudarkodi; Vivek-Ananth, R. P.; Sreejith, R. P.; Mangalapandi, Pattulingam; Hassanali, Ali A.; Samal, Areejit

2018-04-01

We have used molecular dynamics to simulate an amorphous glassy polymer with long chains to study the deformation mechanism of crazing and associated void statistics. The Van der Waals interactions and the entanglements between chains constituting the polymer play a crucial role in crazing. Thus, we have reconstructed two underlying weighted networks, namely, the Van der Waals network and the entanglement network from polymer configurations extracted from the molecular dynamics simulation. Subsequently, we have performed graph-theoretic analysis of the two reconstructed networks to reveal the role played by them in the crazing of polymers. Our analysis captured various stages of crazing through specific trends in the network measures for Van der Waals networks and entanglement networks. To further corroborate the effectiveness of network analysis in unraveling the underlying physics of crazing in polymers, we have contrasted the trends in network measures for Van der Waals networks and entanglement networks in the light of stress-strain behaviour and voids statistics during deformation. We find that the Van der Waals network plays a crucial role in craze initiation and growth. Although, the entanglement network was found to maintain its structure during craze initiation stage, it was found to progressively weaken and undergo dynamic changes during the hardening and failure stages of crazing phenomena. Our work demonstrates the utility of network theory in quantifying the underlying physics of polymer crazing and widens the scope of applications of network science to characterization of deformation mechanisms in diverse polymers.

Dual Cross-Linked Biofunctional and Self-Healing Networks to Generate User-Defined Modular Gradient Hydrogel Constructs.

Science.gov (United States)

Wei, Zhao; Lewis, Daniel M; Xu, Yu; Gerecht, Sharon

2017-08-01

Gradient hydrogels have been developed to mimic the spatiotemporal differences of multiple gradient cues in tissues. Current approaches used to generate such hydrogels are restricted to a single gradient shape and distribution. Here, a hydrogel is designed that includes two chemical cross-linking networks, biofunctional, and self-healing networks, enabling the customizable formation of modular gradient hydrogel construct with various gradient distributions and flexible shapes. The biofunctional networks are formed via Michael addition between the acrylates of oxidized acrylated hyaluronic acid (OAHA) and the dithiol of matrix metalloproteinase (MMP)-sensitive cross-linker and RGD peptides. The self-healing networks are formed via dynamic Schiff base reaction between N-carboxyethyl chitosan (CEC) and OAHA, which drives the modular gradient units to self-heal into an integral modular gradient hydrogel. The CEC-OAHA-MMP hydrogel exhibits excellent flowability at 37 °C under shear stress, enabling its injection to generate gradient distributions and shapes. Furthermore, encapsulated sarcoma cells respond to the gradient cues of RGD peptides and MMP-sensitive cross-linkers in the hydrogel. With these superior properties, the dual cross-linked CEC-OAHA-MMP hydrogel holds significant potential for generating customizable gradient hydrogel constructs, to study and guide cellular responses to their microenvironment such as in tumor mimicking, tissue engineering, and stem cell differentiation and morphogenesis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Grafting functional antioxidants on highly crosslinked polyethylene

Science.gov (United States)

Al-Malaika, S.; Riasat, S.; Lewucha, C.

2016-05-01

The problem of interference of antioxidants, such as hindered phenols, with peroxide-initiated crosslinking of polyethylene was addressed through the use of functional (reactive) graftable antioxidants (g-AO). Reactive derivatives of hindered phenol and hindered amine antioxidants were synthesised, characterised and used to investigate their grafting reactions in high density polyethylene; both non-crosslinked (PE) and highly peroxide-crosslinked (PEXa). Assessment of the extent of in-situ grafting of the antioxidants, their retention after exhaustive solvent extraction in PE and PEXa, and the stabilising performance of the grafted antioxidants (g-AO) in the polymer were examined and benchmarked against conventionally stabilised crosslinked & non-crosslinked polyethylene. It was shown that the functional antioxidants graft to a high extent in PEXa, and that the level of interference of the g-AOs with the polymer crosslinking process was minimal compared to that of conventional antioxidants which bear the same antioxidant function. The much higher level of retention of the g-AOs in PEXa after exhaustive solvent extraction, compared to that of the corresponding conventional antioxidants, accounts for their superior long-term thermal stabilising performance under severe extractive conditions.

Comparison of Polymer Networks Synthesized by Conventional Free Radical and RAFT Copolymerization Processes in Supercritical Carbon Dioxide

Directory of Open Access Journals (Sweden)

Patricia Pérez-Salinas

2017-05-01

Full Text Available There is a debate in the literature on whether or not polymer networks synthesized by reversible deactivation radical polymerization (RDRP processes, such as reversible addition-fragmentation radical transfer (RAFT copolymerization of vinyl/divinyl monomers, are less heterogeneous than those synthesized by conventional free radical copolymerization (FRP. In this contribution, the syntheses by FRP and RAFT of hydrogels based on 2-hydroxyethylene methacrylate (HEMA and ethylene glycol dimethacrylate (EGDMA in supercritical carbon dioxide (scCO2, using Krytox 157 FSL as the dispersing agent, and the properties of the materials produced, are compared. The materials were characterized by differential scanning calorimetry (DSC, swelling index (SI, infrared spectroscopy (FTIR and scanning electron microscopy (SEM. Studies on ciprofloxacin loading and release rate from hydrogels were also carried out. The combined results show that the hydrogels synthesized by FRP and RAFT are significantly different, with apparently less heterogeneity present in the materials synthesized by RAFT copolymerization. A ratio of experimental (Mcexp to theoretical (Mctheo molecular weight between crosslinks was established as a quantitative tool to assess the degree of heterogeneity of a polymer network.

Investigation of Optimum Polymerization Conditions for Synthesis of Cross-Linked Polyacrylamide-Amphoteric Surfmer Nanocomposites for Polymer Flooding in Sandstone Reservoirs

Directory of Open Access Journals (Sweden)

A. N. El-hoshoudy

2015-01-01

Full Text Available Currently enhanced oil recovery (EOR technology is getting more attention by many countries since energy crises are getting worse and frightening. Polymer flooding by hydrophobically associated polyacrylamides (HAPAM and its modified silica nanocomposite are a widely implemented technique through enhanced oil recovery (EOR technology. This polymers class can be synthesized by copolymerization of acrylamide (AM, reactive surfmer, functionalized silica nanoparticles, and a hydrophobic cross-linker moiety in the presence of water soluble initiator via heterogeneous emulsion polymerization technique, to form latexes that can be applied during polymer flooding. Chemical structure of the prepared copolymers was proven through different techniques such as Fourier transform infrared spectroscopy (FTIR, and nuclear magnetic spectroscopy (1H&13C-NMR, and molecular weight was measured by gel permeation chromatography. Study of the effects of monomer, surfmer, cross-linker, silica, and initiator concentrations as well as reaction temperature was investigated to determine optimum polymerization conditions through single factor and orthogonal experiments. Evaluation of the prepared copolymers for enhancing recovered oil amount was evaluated by carrying out flooding experiments on one-dimensional sandstone model to determine recovery factor.

Interpenetrating networks of two conducting polymers

DEFF Research Database (Denmark)

Winther-Jensen, Bjørn; West, Keld

2005-01-01

Interpenetrating networks (IPNs) of two conjugated polymers are prepared by a combination of a chemical oxidation step and a vapour phase polymerisation step on non-conducting surfaces. In this work ferric tosylate was used as the oxidant as it gives very smooth and homogeneous coatings, and beca......Interpenetrating networks (IPNs) of two conjugated polymers are prepared by a combination of a chemical oxidation step and a vapour phase polymerisation step on non-conducting surfaces. In this work ferric tosylate was used as the oxidant as it gives very smooth and homogeneous coatings......, and because its reaction products can be removed efficiently after the formation of the composite. Several combinations of polymers are demonstrated, and the versatility of the proposed method allows extensions to a wide range of conjugated polymers. The IPNs show optical and electrochemical characteristics......, which are sums of the characteristics from the participating conducting polymers....

Radiation crosslinking of poly(butyl acrylate) during polymerization and grafted copolymerization with Cr(III) crosslinked collagen

International Nuclear Information System (INIS)

Pietrucha, K.; Kroh, J.

1984-01-01

Enhanced crosslinking of synthetic polymer simultaneous with grafting and homopolymerization processes have been observed in irradiated leather tanned with Cr(III) and embedded with aqueous emulsions of butyl acrylate. Extent of poly(butyl acrylate) crosslinking during copolymerization was found to be approximately one order higher than in the case of radiation polymerization of butyl acrylate in emulsion. New method for isolation of grafted copolymer based on degradation of collagen has been developed. The extent of crosslinking was calculated from the swelling data. (author)

Synthesis of hydrazone functionalized epoxy polymers for non-linear optical device applications

Science.gov (United States)

Singh, Rajendra K.

A series of twelve, thermally crosslinkable, epoxy polymers bearing covalently attached NLO-active hydrazone chromophores were synthesized. The primary focus was on the synthesis of two series of NLO-active hydroxy functionalized hydrazone chromophores. The first series, called the monohydroxy series (Hydrazones I--VI) comprised of six monohydroxy functionalized hydrazones and the second series consisted of six dihydroxy functionalized hydrazones (Hydrazones VII--XII). These hydrazone chromophores were then grafted, via the hydroxy functionality, on to a commercial epoxy polymer to obtain twelve NLO-active soluble prepolymers. The grafting reaction yields multiple secondary hydroxyl sites due to opening of the epoxide rings and these hydroxyl groups were used for further crosslinking by formulating the prepolymers with a blocked polyisocyanate commercial crosslinker. This formulation was spin coated on glass slides to form 2--2.5 m m thick uniform, defect free, transparent films. The films were corona poled, above their Tg, to align the chromophores in a noncentrosymmetric fashion and simultaneously complete the thermal cure that results in a highly crosslinked network. Finally the thermal characteristics of the second order nonlinearity of the twelve polymers are compared to illustrate the key structure-property relationships underlying the performance of the films.

Crosslinked wholly aromatic polyether membranes based on quinoline derivatives and their application in high temperature polymer electrolyte membrane fuel cells

Science.gov (United States)

Kallitsis, K. J.; Nannou, R.; Andreopoulou, A. K.; Daletou, M. K.; Papaioannou, D.; Neophytides, S. G.; Kallitsis, J. K.

2018-03-01

An AB type difunctional quinoline based monomer bearing a pentafluorophenyl unit combined with a phenol functionality is being synthesized and homopolymerized to create linear aromatic polyethers as polymer electrolytes for HT-PEM FCs applications. Several conditions are tested for the optimized synthesis of the monomer and homopolymer. Additionally, covalent crosslinking through aromatic polyether bond formation enables the creation of wholly aromatic crosslinked polymeric electrolyte membranes. More specifically, the perfluorophenyl units are crosslinked with other hydroxyl end functionalized moieties, providing membranes with enhanced chemical and mechanical properties that are moreover easily doped with phosphoric acid even at ambient temperatures. All membranes are evaluated for their structural and thermal characteristics and their doping ability with phosphoric acid. Selected crosslinked membranes are further tested in terms of their single cell performance at the temperature range 160 °C-200 °C showing promising performance and high conductivity values even up to 0.2 S cm-1 in some cases.

Radiation crosslinking of starch/water-soluble polymer blends for hydrogel

International Nuclear Information System (INIS)

Hashim, K.; Mohid, N.; Bahari, K.; Dahlan, K.Z.

2000-01-01

Water-soluble polymers such as PVP(polyvinyl pyrrolidone) and PVA(polyvinyl alcohol), in aqueous solution can form hydrogel easily upon gamma or electron beam irradiation. The properties of hydrogels, particularly for wound dressing application, can be further improved by adding sago starch to the blend. Results show improved gel strength and elongation properties of the hydrogel with increasing sago concentration. It was found that the PVA/sago hydrogel gives better gel strength and elongation than the PVP/sago hydrogel. The tackiness property of the PVA/sago hydrogel increased with increase amount of sago starch added. In case of PVP/sago hydrogel, the tackiness property shows significant increase with increasing amount of sago except for the 5%PVP composition. The swelling properties of PVP/sago and PVA/sago hydrogel decreased with increasing amount of sago but the crosslink density of the hydrogels also reduced. (author)

Radiation crosslinking of starch/water-soluble polymer blends for hydrogel

Energy Technology Data Exchange (ETDEWEB)

Hashim, K.; Mohid, N.; Bahari, K.; Dahlan, K.Z. [Radiation Processing Technology Division, Malaysian Institute Nuclear Technology Research Malaysia (MINT), Bangi, 43000 Kajang (Malaysia)

2000-03-01

Water-soluble polymers such as PVP(polyvinyl pyrrolidone) and PVA(polyvinyl alcohol), in aqueous solution can form hydrogel easily upon gamma or electron beam irradiation. The properties of hydrogels, particularly for wound dressing application, can be further improved by adding sago starch to the blend. Results show improved gel strength and elongation properties of the hydrogel with increasing sago concentration. It was found that the PVA/sago hydrogel gives better gel strength and elongation than the PVP/sago hydrogel. The tackiness property of the PVA/sago hydrogel increased with increase amount of sago starch added. In case of PVP/sago hydrogel, the tackiness property shows significant increase with increasing amount of sago except for the 5%PVP composition. The swelling properties of PVP/sago and PVA/sago hydrogel decreased with increasing amount of sago but the crosslink density of the hydrogels also reduced. (author)

Pulsed NMR studies of crosslinking and entanglements in high molecular weight linear polydimethylsiloxanes

International Nuclear Information System (INIS)

Folland, R.; Charlesby, A.

1977-01-01

Pulsed NMR studies of proton spin relaxation are used to investigate both radiation-induced cross linking and entanglements in three high molecular weight linear polydimethylsiloxanes (Msub(w) = 26,000, 63,000 and 110,000). Particular emphasis is placed on the spin-spin relaxation since this is determined by the slower relative translational motions of the polymer chains and hence profoundly affected by the presence of intermolecular couplings such as crosslinks or entanglements. The spin-lattice relaxation times, T 1 , are determined by the fast anisotropic chain rotations and are rather insensitive to such intermolecular couplings. The spin-spin relaxation in these materials is represented by a double exponential decay involving two time constants, Tsub(2S) and Tsub(2L). The shorter component, Tsub(2S), is attributed to network material, which may be either of a dynamic form arising from temporary entanglements or of a permanent nature due to crosslinks. The concentration of entanglements depends on the initial molecular weight of the sample whereas the concentration of crosslinks is a function of the radiation dose. The longer component, Tsub(2L), is attributed to the non-network molecules. On the time scale of the NMR measurements the entanglements are shown to act in the same way as crosslinks. The variation of the relative proportions of network and non-network material with dose is shown to be accounted for by using standard gelation theory when allowance is made for the initial effective crosslink density due to entanglements. The analysis provides a value for the average molecular weight per entanglement point of 27,000 +- 1000 which is consistent with the critical molecular weight for entanglements of 29,000. The dependences of Tsub(2S) and Tsub(2L) on dose and molecular weight are also discussed in terms of the molecular motion. (author)

New crosslinked polyvinyl chloride insulated wire by electron beam irradiation

International Nuclear Information System (INIS)

Takahata, Norio; Shingyouchi, Kazuo; Sato, Masakatsu; Sasaki, Hidemi; Terunuma, Haruji

1978-01-01

The polyvinyl chloride-coated wires crosslinked by electron beam irradiation have made rapid progress as electric and electronic wiring material and grown to hold a firm position in this field. In response to the requirements for wires with the advance of electronic equipments, Hitachi Cable Ltd. developed a peculiar graft polymer consisting of chlorinated polyethylene and polyvinyl chloride. To this polymer, the characteristics of a very wide range from toughness to flexibility can be given, and the crosslinked polyvinyl chloride wires utilizing these characteristics were put in practical use. Many kinds of the wires were developed as follows; 105 deg. C rating crosslinked vinyl-coated wires authorized by UL and CSA standards, crosslinked vinyl-coated wires with excellent flexibility, high strength crosslinked vinyl-coated wires with thin coating and crosslinked vinyl-coated wires for automobiles. They are expected to be developed into other new fields and applications. (Kobatake, H.)

Radiation crosslinking of poly(butyl acrylate) during polymerization and grafted copolymerization with Cr(III) crosslinked collagen

International Nuclear Information System (INIS)

Pietrucha, K.; Kroh, J.

1986-01-01

Enhanced crosslinking of synthetic polymer simultaneously with grafting and homopolymerization processes has been observed in irradiated leather tanned with Cr(III) and embedded with aqueous emulsions of butyl acrylate. The extent of poly(butyl acrylate) crosslinking during copolymerization was found to be approximately one order higher than in the case of radiation polymerization of butyl acrylate in emulsion. A new method for isolation of grafted copolymer based on degradation of collagen has been developed. The extent of crosslinking was calculated from the swelling data. (author)

Tracer diffusion in a polymer gel: simulations of static and dynamic 3D networks using spherical boundary conditions

International Nuclear Information System (INIS)

Kamerlin, Natasha; Elvingson, Christer

2016-01-01

We have investigated an alternative to the standard periodic boundary conditions for simulating the diffusion of tracer particles in a polymer gel by performing Brownian dynamics simulations using spherical boundary conditions. The gel network is constructed by randomly distributing tetravalent cross-linking nodes and connecting nearest pairs. The final gel structure is characterised by the radial distribution functions, chain lengths and end-to-end distances, and the pore size distribution. We have looked at the diffusion of tracer particles with a wide range of sizes, diffusing in both static and dynamic networks of two different volume fractions. It is quantitatively shown that the dynamical effect of the network becomes more important in facilitating the diffusional transport for larger particle sizes, and that one obtains a finite diffusion also for particle sizes well above the maximum in the pore size distribution. (paper)

Properties of crosslinked ultra-high-molecular-weight polyethylene.

Science.gov (United States)

Lewis, G

2001-02-01

Substantially reducing the rate of generation of wear particles at the surfaces of ultra-high-molecular-weight polyethylene (UHMWPE) orthopedic implant bearing components, in vivo, is widely regarded as one of the most formidable challenges in modern arthroplasty. In the light of this, much research attention has been paid to the myriad of endogenous and exogenous factors that have been postulated to affect this wear rate, one such factor being the polymer itself. In recent years, there has been a resurgence of interest in crosslinking the polymer as a way of improving its properties that are considered relevant to its use for fabricating bearing components. Such properties include wear resistance, fatigue life, and fatigue crack propagation rate. Although a large volume of literature exists on the topic on the impact of crosslinking on the properties of UHMWPE, no critical appraisal of this literature has been published. This is one of the goals of the present article, which emphasizes three aspects. The first is the trade-off between improvement in wear resistance and depreciation in other mechanical and physical properties. The second aspect is the presentation of a method of estimating the optimal value of a crosslinking process variable (such as dose in radiation-induced crosslinking) that takes into account this trade-off. The third aspect is the description of a collection of under- and unexplored research areas in the field of crosslinked UHMWPE, such as the role of starting resin on the properties of the crosslinked polymer, and the in vitro evaluation of the wear rate of crosslinked tibial inserts and other bearing components that, in vivo, are subjected to nearly unidirectional motion.

Radiation induced crosslinking of cellulose ethers

International Nuclear Information System (INIS)

Wach, A.R.; Mitomo, H.; Yoshii, F.; Kume, T.

2002-01-01

The effects of high-energy radiation on four ethers of cellulose: carboxymethyl (CMC); hydroxypropyl (HPC), hydroxyethyl (HEC) and methylcellulose (MC) were investigated. Polymers are irradiated in solid state and in aqueous solutions at various concentrations. Degree of substitution (DS) of the derivatives, the concentration of their aqueous solutions and irradiation conditions had a significant impact on the obtained products. Irradiation of polymers in solid state and in diluted aqueous solutions resulted in their degradation. However, it was found that for concentrated solutions gel formation occurred. Paste-like form of the initial material, when water plasticizes the bulk of polymer as well as the high dose rate, what prevents oxygen penetration of the polymer during irradiation, have been found favourable for hydrogel formation. Up to 95% of gel fraction was obtained from solutions of CMC with concentration over 50% irradiated by γ-rays or electron beam. It was pointed out that the ability to the formation of the three-dimensional network is related to the DS of anhydroglucose units and a type of chemical group introduced to main chain of cellulose. Produced hydrogels swelled markedly in water. Despite of the crosslinked structure they underwent degradation by the action of cellulase enzyme or microorganisms from compost, and can be included into the group of biodegradable materials. (author)

Development of semi- and grafted interpenetrating polymer networks based on poly(ethylene glycol) diacrylate and collagen.

Science.gov (United States)

Madaghiele, Marta; Marotta, Francesco; Demitri, Christian; Montagna, Francesco; Maffezzoli, Alfonso; Sannino, Alessandro

2014-12-30

The objective of this work was to develop composite hydrogels based on poly(ethylene glycol) diacrylate (PEGDA) and collagen (Coll), potentially useful for biomedical applications. Semi-interpenetrating polymer networks (semi-IPNs) were obtained by photo-stabilizing aqueous solutions of PEGDA and acrylic acid (AA), in the presence of collagen. Further grafting of the collagen macromolecules to the PEGDA/poly(AA) network was achieved by means of a carbodiimide-mediated crosslinking reaction. The resulting hydrogels were characterized in terms of swelling capability, collagen content and mechanical properties. The grafting procedure was found to significantly improve the mechanical stability of the IPN hydrogels, due to the establishment of covalent bonding between the PEGDA/poly(AA) and the collagen networks. The suitability of the composite hydrogels to be processed by means of stereolithography (SLA) was also investigated, toward creating biomimetic constructs with complex shapes, which might be useful either as platforms for tissue engineering applications or as tissue mimicking phantoms.

Shape-memory properties of magnetically active triple-shape nanocomposites based on a grafted polymer network with two crystallizable switching segments

Directory of Open Access Journals (Sweden)

A. Lendlein

2012-01-01

Full Text Available Thermo-sensitive shape-memory polymers (SMP, which are capable of memorizing two or more different shapes, have generated significant research and technological interest. A triple-shape effect (TSE of SMP can be activated e.g. by increasing the environmental temperature (Tenv, whereby two switching temperatures (Tsw have to be exceeded to enable the subsequent shape changes from shape (A to shape (B and finally the original shape (C. In this work, we explored the thermally and magnetically initiated shape-memory properties of triple-shape nanocomposites with various compositions and particle contents using different shape-memory creation procedures (SMCP. The nanocomposites were prepared by the incorporation of magnetite nanoparticles into a multiphase polymer network matrix with grafted polymer network architecture containing crystallizable poly(ethylene glycol (PEG side chains and poly(ε-caprolactone (PCL crosslinks named CLEGC. Excellent triple-shape properties were achieved for nanocomposites with high PEG weight fraction when two-step programming procedures were applied. In contrast, single-step programming resulted in dual-shape properties for all investigated materials as here the temporary shape (A was predominantly fixed by PCL crystallites.

Light-induced cross-linking and post-cross-linking modification of polyglycidol.

Science.gov (United States)

Marquardt, F; Bruns, M; Keul, H; Yagci, Y; Möller, M

2018-02-08

The photoinduced radical generation process has received renewed interest due to its economic and ecological appeal. Herein the light-induced cross-linking of functional polyglycidol and its post-cross-linking modification are presented. Linear polyglycidol was first functionalized with a tertiary amine in a two-step reaction. Dimethylaminopropyl functional polyglycidol was cross-linked in a UV-light mediated reaction with camphorquinone as a type II photoinitiator. The cross-linked polyglycidol was further functionalized by quaternization with various organoiodine compounds. Aqueous dispersions of the cross-linked polymers were investigated by means of DLS and zeta potential measurements. Polymer films were evaluated by DSC and XPS.

Protein permeation through polymer membranes for hybrid-type artificial pancreas

Energy Technology Data Exchange (ETDEWEB)

Burczak, K; Fujisato, Toshiya; Ikada, Yoshito [Kyoto Univ. (Japan); Hatada, Motoyoshi

1991-05-01

Hydrogel membranes were prepared by radiation crosslinking of poly (vinyl alcohol) (PVA) in aqueous solutions. Effects of PVA concentration, PVA molecular weight, and radiation dose on the permeation of insulin and immunoglobulin through the membranes were investigated. Glucose permeation was also studied. The crosslinking density affected the size of macromolecular mesh of hydrogel network as well as the water content of membrane responsible for the diffusion of the solutes. The diffusion coefficient linearly increased for all the solutes with the increasing water content in PVA hydrogels, indicating that diffusion occurs primarily through the water hydrating the polymer network. The increase in crosslinking density of hydrogels by changing PVA molecular weight brought about the decrease in mesh size of the hydrogels, which, in turn, had an influence on the diffusion of immunoglobulin, but not of insulin and glucose. (author).

Biohybrid Fibro-Porous Vascular Scaffolds: Effect of Crosslinking on Properties

OpenAIRE

Thomas, Vinoy; Nozik, Danna; Patel, Harsh; Singh, Raj K.; Vohra, Yogesh K.

2015-01-01

Tubular grafts were fabricated from blends of polycaprolactone (PCL) and poly(glycolide -co-caprolactone) (PGC) polymers and coated with an extracellular matrix containing collagens, laminin, and proteoglycans, but not growth factors (HuBiogel™). Multifunctional scaffolds from polymer blends and membrane proteins provide the necessary biomechanics and biological functions for tissue regeneration. Two crosslinking agents, a natural crosslinker namely genipin (Gp) and a carbodiimide reagent nam...

Removal of anionic azo dyes from aqueous solution by functional ionic liquid cross-linked polymer

International Nuclear Information System (INIS)

Gao, Hejun; Kan, Taotao; Zhao, Siyuan; Qian, Yixia; Cheng, Xiyuan; Wu, Wenli; Wang, Xiaodong; Zheng, Liqiang

2013-01-01

Highlights: • Equilibrium, kinetic and thermodynamic of adsorption of dyes onto PDVB-IL was investigated. • PDVB-IL has a high adsorption capacity to treat dyes solution. • Higher adsorption capacity is due to the functional groups of PDVB-IL. • Molecular structure of dyes influences the adsorption capacity. -- Abstract: A novel functional ionic liquid based cross-linked polymer (PDVB-IL) was synthesized from 1-aminoethyl-3-vinylimidazolium chloride and divinylbenzene for use as an adsorbent. The physicochemical properties of PDVB-IL were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The adsorptive capacity was investigated using anionic azo dyes of orange II, sunset yellow FCF, and amaranth as adsorbates. The maximum adsorption capacity could reach 925.09, 734.62, and 547.17 mg/g for orange II, sunset yellow FCF and amaranth at 25 °C, respectively, which are much better than most of the other adsorbents reported earlier. The effect of pH value was investigated in the range of 1–8. The result shows that a low pH value is found to favor the adsorption of those anionic azo dyes. The adsorption kinetics and isotherms are well fitted by a pseudo second-order model and Langmuir model, respectively. The adsorption process is found to be dominated by physisorption. The introduction of functional ionic liquid moieties into cross-linked poly(divinylbenzene) polymer constitutes a new and efficient kind of adsorbent

Desorption of 3,3′-diindolylmethane from imprinted particles: An impact of cross-linker structure on binding capacity and selectivity

Energy Technology Data Exchange (ETDEWEB)

Klejn, Dorota; Luliński, Piotr; Maciejewska, Dorota, E-mail: dorota.maciejewska@wum.edu.pl

2015-11-01

Here, seven cross-linkers (six polar diacrylates or dimethacrylates of different lengths between double bonds, and one aromatic-divinylbenzene) were used to examine the impact of the cross-linker on binding capacity and selectivity of 3,3′-diindolylmethane (DIM) imprinted material. DIM participates in the suppression of viability of human ovarian and human breast cancer cell lines, but has low bioavailability. The investigations of novel imprinted polymer matrices for improvement of DIM release could allow to utilize not only a potency of DIM but also similar alkaloids, which are the important compounds with pharmacological activity. The bulk, thermal radical copolymerization of the cross-linkers in the presence of 3,3′-diindolylmethane (the template) and allylamine (the functional monomer) in dimethyl sulfoxide or in carbon tetrachloride (porogens) was carried out. The binding capacities of imprinted and non-imprinted polymers were compared, and two polymers (these were prepared using ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate as the cross-linkers) with the highest selectivity and binding capacity were selected to desorption test. The desorption profile of polymer prepared using polyethylene glycol dimethacrylate as the cross-linker revealed sustained release of 3,3′-diindolylmethane, and this system was selected for further optimization of the cross-linker amounts. The morphology and structure of the selected particles were analyzed using SEM micrographs, {sup 13}C CP/MAS NMR spectroscopy, and BET measurements. The desorption of 3,3′-diindolylmethane from poly(allylamine-co-polyethylene glycol dimethacrylate) particles was in accordance with pseudo-second-order kinetics and the simplified Higuchi model indicated the diffusion controlled release of 3,3′-diindolylmethane. - Graphical abstract: Sustained release of 3,3′-diindolylmethane from cavity in imprinted poly(allylamine-co-polyethylene glycol dimethacrylate

Desorption of 3,3′-diindolylmethane from imprinted particles: An impact of cross-linker structure on binding capacity and selectivity

International Nuclear Information System (INIS)

Klejn, Dorota; Luliński, Piotr; Maciejewska, Dorota

2015-01-01

Here, seven cross-linkers (six polar diacrylates or dimethacrylates of different lengths between double bonds, and one aromatic-divinylbenzene) were used to examine the impact of the cross-linker on binding capacity and selectivity of 3,3′-diindolylmethane (DIM) imprinted material. DIM participates in the suppression of viability of human ovarian and human breast cancer cell lines, but has low bioavailability. The investigations of novel imprinted polymer matrices for improvement of DIM release could allow to utilize not only a potency of DIM but also similar alkaloids, which are the important compounds with pharmacological activity. The bulk, thermal radical copolymerization of the cross-linkers in the presence of 3,3′-diindolylmethane (the template) and allylamine (the functional monomer) in dimethyl sulfoxide or in carbon tetrachloride (porogens) was carried out. The binding capacities of imprinted and non-imprinted polymers were compared, and two polymers (these were prepared using ethylene glycol dimethacrylate and polyethylene glycol dimethacrylate as the cross-linkers) with the highest selectivity and binding capacity were selected to desorption test. The desorption profile of polymer prepared using polyethylene glycol dimethacrylate as the cross-linker revealed sustained release of 3,3′-diindolylmethane, and this system was selected for further optimization of the cross-linker amounts. The morphology and structure of the selected particles were analyzed using SEM micrographs, 13 C CP/MAS NMR spectroscopy, and BET measurements. The desorption of 3,3′-diindolylmethane from poly(allylamine-co-polyethylene glycol dimethacrylate) particles was in accordance with pseudo-second-order kinetics and the simplified Higuchi model indicated the diffusion controlled release of 3,3′-diindolylmethane. - Graphical abstract: Sustained release of 3,3′-diindolylmethane from cavity in imprinted poly(allylamine-co-polyethylene glycol dimethacrylate). - Highlights: �

FTIR spectroscopy and thermodynamics of hydrogen adsorbed in a cross-linked polymer.

Science.gov (United States)

Spoto, Giuseppe; Vitillo, Jenny G; Cocina, Donato; Damin, Alessandro; Bonino, Francesca; Zecchina, Adriano

2007-09-28

The adsorption of H(2) in a cross-linked poly(styrene-co-divinylbenzene) (St-DVB) microporous polymer (BET surface area 920 m(2) g(-1)) is studied by volumetric and gravimetric methods, FTIR spectroscopy at variable temperature (300-14 K) and ab initio calculations. At 77 K the polymer reversibly stores up to 1.3 mass% H(2) at a pressure of 1 bar and 1.8 mass% at 10 bar. The adsorption process involves the specific interaction of H(2) with the structural phenyl rings through weak dispersive forces. The interacting molecules become IR active and give rise to vibrational and rotational-vibrational manifestations which are affected by the temperature, the contact time and the H(2) equilibrium pressure. The spectra of the H(2)/St-DVB system reported here represent the first IR evidence of the adsorption of hydrogen on unsaturated molecules. The adsorption enthalpy is evaluated by the VTIR (variable temperature IR spectroscopy) method (C. Otero Areán et al., Phys. Chem. Chem. Phys., 2007, DOI: 10.1039/b615535a) and compared with the results of ab initio calculations for the H(2)/benzene interaction and with literature data.

Inclusion and Functionalization of Polymers with Cyclodextrins: Current Applications and Future Prospects

Directory of Open Access Journals (Sweden)

Christian Folch-Cano

2014-09-01

Full Text Available The numerous hydroxyl groups available in cyclodextrins are active sites that can form different types of linkages. They can be crosslinked with one another, or they can be derivatized to produce monomers that can form linear or branched networks. Moreover, they can form inclusion complexes with polymers and different substrates, modifying their physicochemical properties. This review shows the different applications using polymers with cyclodextrins, either by forming inclusion complexes, ternary complexes, networks, or molecularly imprinted polymers (MIPs. On one hand, the use of cyclodextrins enhances the properties of each polymer, and on the other the use of polymers decreases the amount of cyclodextrins required in different formulations. Both cyclodextrins and polymers contribute synergistically in several applications such as pharmacological, nutritional, environmental, and other industrial fields. The use of polymers based on cyclodextrins is a low cost easy to use potential tool with great future prospects.

The Reverse Thermal Effect in Epoxy Resins and Moisture Absorption in Semi-Interpenetrating Polymer Networks.

Science.gov (United States)

El-Sa'Ad, Leila

1989-12-01

Available from UMI in association with The British Library. Requires signed TDF. Epoxy resins exhibit many desirable properties which make them ideal subjects for use as matrices of composite materials in many commercial, military and space applications. However, due to their high cross-link density they are often brittle. Epoxy resin networks have been modified by incorporating tough, ductile thermoplastics. Such systems are referred to as Semi-Interpenetrating Polymer Networks (Semi-IPN). Systematic modification to the thermoplastics backbone allowed the morphology of the blend to be controlled from a homogeneous one-phase structure to fully separated structures. The moisture absorption by composites in humid environments has been found to lead to a deterioration in the physical and mechanical properties of the matrix. Therefore, in order to utilize composites to their full potential, their response to hot/wet environments must be known. The aims of this investigation were two-fold. Firstly, to study the effect of varying the temperature of exposure at different stages in the absorption process on the water absorption behaviour of a TGDDM/DDS epoxy resin system. Secondly, to study water absorption characteristics, under isothermal conditions, of Semi-Interpenetrating Polymer Networks possessing different morphologies, and develop a theoretical model to evaluate the diffusion coefficients of the two-phase structures. The mathematical treatment used in this analysis was based on Fick's second law of diffusion. Tests were performed on specimens immersed in water at 10 ^circ, 40^circ and 70^circC, their absorption behaviour and swelling behaviour, as a consequence of water absorption, were investigated. The absorption results of the variable temperature absorption tests indicated a saturation dependence on the absorption behaviour. Specimens saturated at a high temperature will undergo further absorption when transferred to a lower temperature. This behaviour was

High-Temperature Shape Memory Polymers

Science.gov (United States)

Yoonessi, Mitra; Weiss, Robert A.

2012-01-01

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing

Temperature dependence of electrochemical properties of cross-linked poly(ethylene oxide)–lithium bis(trifluoromethanesulfonyl)imide–N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide solid polymer electrolytes for lithium batteries

International Nuclear Information System (INIS)

Wetjen, Morten; Kim, Guk-Tae; Joost, Mario; Winter, Martin; Passerini, Stefano

2013-01-01

Highlights: ► Solid-state electrolyte for lithium batteries. ► Polymer electrolyte with improved mechanical properties by cross-linking. ► Enhanced performance of polymer electrolytes using water- and air-stable ionic liquids as co-salts. ► Polymer electrolyte with high rate capability at moderate temperatures. - Abstract: An advanced electrochemical characterization of cross-linked ternary solid polymer electrolytes (SPEs), prepared by a solvent-free hot-pressing process, is reported. Ionic conductivity, electrochemical stability window and limiting current measurements were performed as a function of the temperature by using both potentiodynamic and galvanostatic techniques. Additionally, the lithium cycleability was evaluated with respect to its dependence on both the operating temperature and the current density by using a new multi-rate Li-stripping-plating procedure. The results clearly indicate the beneficial effect of higher operating temperatures on the rate-capability, without major degradation of the electrochemical stability of the SPE. All-solid-state lithium metal polymer batteries (LMPBs), comprising a lithium metal anode, the cross-linked ternary solid polymer electrolyte and a LiFePO 4 composite cathode, were manufactured and investigated in terms of the interdependencies of the delivered capacity, operating temperature and discharge rate. The results prove quite exceptional delivered capacities both at medium current densities at ambient temperatures and even more impressive capacities above 160 mAh g −1 at high discharge rates (1 C) and temperatures above 60 °C.

Surface morphological modification of crosslinked hydrophilic co-polymers by nanosecond pulsed laser irradiation

Energy Technology Data Exchange (ETDEWEB)

Primo, Gastón A.; Alvarez Igarzabal, Cecilia I. [IMBIV (CONICET), Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Haya de la Torre y Medina Allende, Edificio de Ciencias II, Ciudad Universitaria, Córdoba X5000HUA (Argentina); Pino, Gustavo A.; Ferrero, Juan C. [INFIQC (CONICET), Departamento de Fisicoquímica, Facultad de Ciencias Químicas, and Centro Láser de Ciencias Moleculares, Universidad Nacional de Córdoba, Córdoba X5000IUS (Argentina); Rossa, Maximiliano, E-mail: mrossa@fcq.unc.edu.ar [INFIQC (CONICET), Departamento de Fisicoquímica, Facultad de Ciencias Químicas, and Centro Láser de Ciencias Moleculares, Universidad Nacional de Córdoba, Córdoba X5000IUS (Argentina)

2016-04-30

Graphical abstract: - Highlights: • Laser-induced surface modification of crosslinked hydrophilic co-polymers by ns pulses. • Formation of ablation craters observed under most of the single-pulse experimental conditions. • UV laser foaming of dried hydrogel samples resulting from single- and multiple-pulse experiments. • Threshold values of the incident laser fluence reported for the observed surface modifications. • Lower threshold fluences for acrylate-based, compared to acrylamide-based hydrogels. - Abstract: This work reports an investigation of the surface modifications induced by irradiation with nanosecond laser pulses of ultraviolet and visible wavelengths on crosslinked hydrophilic co-polymeric materials, which have been functionalized with 1-vinylimidazole as a co-monomer. A comparison is made between hydrogels differing in the base co-monomer (N,N-dimethylaminoethyl methacrylate and N-[3-(dimethylamino)propyl] methacrylamide) and in hydration state (both swollen and dried states). Formation of craters is the dominant morphological change observed by ablation in the visible at 532 nm, whereas additional, less aggressive surface modifications, chiefly microfoams and roughness, are developed in the ultraviolet at 266 nm. At both irradiation wavelengths, threshold values of the incident laser fluence for the observation of the various surface modifications are determined under single-pulse laser irradiation conditions. It is shown that multiple-pulse irradiation at 266 nm with a limited number of laser shots can be used alternatively for generating a regular microfoam layer at the surface of dried hydrogels based on N,N-dimethylaminoethyl methacrylate. The observations are rationalized on the basis of currently accepted mechanisms for laser-induced polymer surface modification, with a significant contribution of the laser foaming mechanism. Prospective applications of the laser-foamed hydrogel matrices in biomolecule immobilization are suggested.

Nanofiltration membranes based on polyvinylidene fluoride nanofibrous scaffolds and crosslinked polyethyleneimine networks

Energy Technology Data Exchange (ETDEWEB)

Park, Seong-Jik [Hankyong National University, Department of Bioresources and Rural Systems Engineering (Korea, Republic of); Cheedrala, Ravi Kumar; Diallo, Mamadou S., E-mail: mdiallo@kaist.ac.kr [Korea Advanced Institute of Science and Technology (KAIST), Graduate School of Energy, Environment, Water and Sustainability (EEWS) (Korea, Republic of); Kim, Changmin; Kim, In S. [Gwangju Institute of Science and Technology (GIST), Department of Environmental Science and Engineering (Korea, Republic of); Goddard, William A. [Korea Advanced Institute of Science and Technology (KAIST), Graduate School of Energy, Environment, Water and Sustainability (EEWS) (Korea, Republic of)

2012-07-15

In this article, we describe the synthesis of new and ion-selective nanofiltration (NF) membranes using polyvinylidene fluoride (PVDF) nanofibers and hyperbranched polyethylenimine (PEI) as building blocks. These new nanofibrous composite (NFC) membranes consist of crosslinked hyperbranched PEI networks supported by PVDF nanofibrous scaffolds that are electrospun onto commercial PVDF microfiltration (MF) membranes. A major objective of our study was to fabricate positively charged NF membranes that can be operated at low pressure with high water flux and improved rejection for monovalent cations. To achieve this, we investigated the effects of crosslinker chemistry on membrane properties (morphology, composition, hydrophobicity, and zeta potential) and membrane performance (salt rejection and permeate flux) in aqueous solutions (2,000 mg/L) of four salts (NaCl, MgCl{sub 2}, Na{sub 2}SO{sub 4}, and MgSO{sub 4}) at pH 4, 6, and 8. We found that an NFC-PVDF membrane with a network of PEI macromolecules crosslinked with trimesoyl chloride has a high water flux ({approx}30 L m{sup -2} h{sup -1}) and high rejections for MgCl{sub 2} ({approx}88 %) and NaCl ({approx}65 %) at pH 6 using a pressure of 7 bar. The overall results of our study suggest that PVDF nanofibers and hyperbranched PEI are promising building blocks for the fabrication of high performance NF membranes for water purification.

Nanofiltration membranes based on polyvinylidene fluoride nanofibrous scaffolds and crosslinked polyethyleneimine networks

International Nuclear Information System (INIS)

Park, Seong-Jik; Cheedrala, Ravi Kumar; Diallo, Mamadou S.; Kim, Changmin; Kim, In S.; Goddard, William A.

2012-01-01

In this article, we describe the synthesis of new and ion-selective nanofiltration (NF) membranes using polyvinylidene fluoride (PVDF) nanofibers and hyperbranched polyethylenimine (PEI) as building blocks. These new nanofibrous composite (NFC) membranes consist of crosslinked hyperbranched PEI networks supported by PVDF nanofibrous scaffolds that are electrospun onto commercial PVDF microfiltration (MF) membranes. A major objective of our study was to fabricate positively charged NF membranes that can be operated at low pressure with high water flux and improved rejection for monovalent cations. To achieve this, we investigated the effects of crosslinker chemistry on membrane properties (morphology, composition, hydrophobicity, and zeta potential) and membrane performance (salt rejection and permeate flux) in aqueous solutions (2,000 mg/L) of four salts (NaCl, MgCl 2 , Na 2 SO 4 , and MgSO 4 ) at pH 4, 6, and 8. We found that an NFC–PVDF membrane with a network of PEI macromolecules crosslinked with trimesoyl chloride has a high water flux (∼30 L m −2 h −1 ) and high rejections for MgCl 2 (∼88 %) and NaCl (∼65 %) at pH 6 using a pressure of 7 bar. The overall results of our study suggest that PVDF nanofibers and hyperbranched PEI are promising building blocks for the fabrication of high performance NF membranes for water purification.

The application of radiothermoluminescence method to the analysis of polymers and polymer composites

International Nuclear Information System (INIS)

Nikol'skii, V.G.

1982-01-01

The basic results concerning the examination of copolymers, cross-linked polymers and polyblends structure, obtained by means of radiothermoluminescence method, are reviewed. The main emphasis is on the glow curve shape analysis that allows: a) to determine quantitatively the random copolymer composition; b) to reveal the existence of blocks in macromolecules; c) to examine the grafted copolymer distribution in polymer matrix; d) to estimate the degree of cross-linking both for individual polymers and heterogeneous polyblends; e) to study the mutual solubility of polymers. (author)

Dynamics of a Novel Class of Polymers: Polymerized Sulfur

Science.gov (United States)

Masser, Kevin; Kim, Jenny; Oleshko, Vladimir; Griebel, Jared; Chung, Woo; Simmons, Adam; Pyun, Jeff; Soles, Christopher

2013-03-01

In this study we investigate the dynamics of a new type of polymer, consisting mainly of sulfur. Room-temperature stable polymerized sulfur samples were prepared by crosslinking the well-known living sulfur polymers formed at elevated temperatures by the addition of a crosslinking agent. This reverse vulcanization process was used to create a series of samples with different amounts of crosslinking agent. These polymers show great promise for use in advanced batteries as cathode materials. Each system exhibits a glassy-state beta relaxation, with the intensity of this relaxation proportional to the crosslinking content. A dynamic glass transition is also observed for each system, and the glass transition temperature/segmental relaxation moves to higher temperatures with increased crosslink content as is typically observed in crosslinked systems. As is typical of polymers, ion motion in these systems is closely coupled to the backbone motion of the host polymer. National Research Council Postdoctoral Fellowship

Synthesis and characterization of a new photo-crosslinkable glycol chitosan thermogel for biomedical applications.

Science.gov (United States)

Cho, Ik Sung; Cho, Myeong Ok; Li, Zhengzheng; Nurunnabi, Md; Park, Sung Young; Kang, Sun-Woong; Huh, Kang Moo

2016-06-25

The major limitations of typical thermogelling polymers for practical applications are low gel stability and weak mechanical properties under physiological conditions. In this study, we have synthesized a new polysaccharide-based thermogelling polymer that can be photo-crosslinked by UV irradiation to form a mechanically resilient and elastic hydrogel. Methacrylated hexanoyl glycol chitosan (M-HGC), was synthesized by a series of chemical modifications, N-hexanoylation and N-methacrylation, of glycol chitosan (GC). Various M-HGC polymers with different methacryl group contents were synthesized and their thermogelling and photo-crosslinkable properties were evaluated. The M-HGCs demonstrated a thermo-reversible sol-gel transition behavior in aqueous solutions. The thermally-induced hydrogels could be chemically crosslinked by UV-triggered photo-crosslinking. From the cytotoxicity studies using MTT and the live/dead assay, the M-HGC hydrogels showed non-cytotoxicity. These photo-crosslinkable thermogelling M-HGC polymers may hold great promises for various biomedical applications, such as an injectable delivery system and 3D cell culture. Copyright © 2016 Elsevier Ltd. All rights reserved.

Selective removal of heavy metal ions by disulfide linked polymer networks

Energy Technology Data Exchange (ETDEWEB)

Ko, Dongah [Department of Environmental Engineering, Technical University of Denmark, Miljøvej 113, 2800 Kgs. Lyngby (Denmark); Lee, Joo Sung [Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141 (Korea, Republic of); Patel, Hasmukh A. [Department of Chemistry, Northwestern University, Evanston, IL 60208 (United States); Jakobsen, Mogens H. [Department of Micro and Nano technology, Technical University of Denmark, Ørsteds Plads, 345B, 2800 Kgs. Lyngby (Denmark); Hwang, Yuhoon [Department of Environmental Engineering, Seoul National University of Science and Technology, 232 Gongreung-ro, Nowon-gu, Seoul 01811 (Korea, Republic of); Yavuz, Cafer T. [Graduate School of EEWS, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141 (Korea, Republic of); Hansen, Hans Chr. Bruun [Department of Plant and Environmental Sciences, University of Copenhagen, Frederiksberg, Thorvaldsensvej 40, 1871 Frederiksberg C (Denmark); Andersen, Henrik R., E-mail: henrik@ndersen.net [Department of Environmental Engineering, Technical University of Denmark, Miljøvej 113, 2800 Kgs. Lyngby (Denmark)

2017-06-15

Highlights: • Disulfide/thiol polymer networks are promising as sorbent for heavy metals. • Rapid sorption and high Langmuir affinity constant (a{sub L}) for stormwater treatment. • Selective sorption for copper, cadmium, and zinc in the presence of calcium. • Reusability likely due to structure stability of disulfide linked polymer networks. - Abstract: Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions–copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water.

Covalent crosslinking of carbon nanostructures

Indian Academy of Sciences (India)

Composites of the binary conjugates with polymer can be readily prepared by using the ... Besides the preparation of crosslinked ... of graphite oxide following the procedure described ... several times to remove the metal nanoparticles and.

Non-Linear Behaviour Of Gelatin Networks Reveals A Hierarchical Structure

KAUST Repository

Yang, Zhi; Hemar, Yacine; Hilliou, loic; Gilbert, Elliot P.; McGillivray, Duncan James; Williams, Martin A. K.; Chaieb, Saharoui

2015-01-01

We investigate the strain hardening behaviour of various gelatin networks - namely physically-crosslinked gelatin gel, chemically-crosslinked gelatin gels, and a hybrid gels made of a combination of the former two - under large shear deformations using the pre-stress, strain ramp, and large amplitude oscillation shear protocols. Further, the internal structures of physically-crosslinked gelatin gel and chemically-crosslinked gelatin gels were characterized by small angle neutron scattering (SANS) to enable their internal structures to be correlated with their nonlinear rheology. The Kratky plots of SANS data demonstrate the presence of small cross-linked aggregates within the chemically-crosslinked network, whereas in the physically-crosslinked gels a relatively homogeneous structure is observed. Through model fitting to the scattering data, we were able to obtain structural parameters, such as correlation length (ξ), cross-sectional polymer chain radius (Rc), and the fractal dimension (df) of the gel networks. The fractal dimension df obtained from the SANS data of the physically-crosslinked and chemically crosslinked gels is 1.31 and 1.53, respectively. These values are in excellent agreement with the ones obtained from a generalized non-linear elastic theory we used to fit our stress-strain curves. The chemical crosslinking that generates coils and aggregates hinders the free stretching of the triple helices bundles in the physically-crosslinked gels.

Non-Linear Behaviour Of Gelatin Networks Reveals A Hierarchical Structure

KAUST Repository

Yang, Zhi

2015-12-14

We investigate the strain hardening behaviour of various gelatin networks - namely physically-crosslinked gelatin gel, chemically-crosslinked gelatin gels, and a hybrid gels made of a combination of the former two - under large shear deformations using the pre-stress, strain ramp, and large amplitude oscillation shear protocols. Further, the internal structures of physically-crosslinked gelatin gel and chemically-crosslinked gelatin gels were characterized by small angle neutron scattering (SANS) to enable their internal structures to be correlated with their nonlinear rheology. The Kratky plots of SANS data demonstrate the presence of small cross-linked aggregates within the chemically-crosslinked network, whereas in the physically-crosslinked gels a relatively homogeneous structure is observed. Through model fitting to the scattering data, we were able to obtain structural parameters, such as correlation length (ξ), cross-sectional polymer chain radius (Rc), and the fractal dimension (df) of the gel networks. The fractal dimension df obtained from the SANS data of the physically-crosslinked and chemically crosslinked gels is 1.31 and 1.53, respectively. These values are in excellent agreement with the ones obtained from a generalized non-linear elastic theory we used to fit our stress-strain curves. The chemical crosslinking that generates coils and aggregates hinders the free stretching of the triple helices bundles in the physically-crosslinked gels.

Radiation preparation of interpenetrating polymer networks

International Nuclear Information System (INIS)

Sheikh, N.; Ahmadi, M.; Afshar Taromi, F.

2002-01-01

Sequential interpenetrating polymer netwoks were prepared using gamma radiation. Styrene-butadiene rubber (SBR) and polymethyl methacrylate (PMMA) were used as elastomer and plastomer components respectively. Dicumyl peroxide (DCP) and ethylene glycol dimethacrylate (EGDMA) were also used as the curing agent of SBR and crosslinker for MMA monomer. The resulting IPNs were characterized by evaluating their mechanical properties. The effect of the amount of DCP on the final properties of product was examined. It was found that amount of curing agent had an important role on the properties of obtained IPNS. The results of the mechanical properties of IPNs showed very good synergistic behavior. (Author)

Antimocrobial Polymer

Science.gov (United States)

McDonald, William F.; Huang, Zhi-Heng; Wright, Stacy C.

2005-09-06

A polymeric composition having antimicrobial properties and a process for rendering the surface of a substrate antimicrobial are disclosed. The composition comprises a crosslinked chemical combination of (i) a polymer having amino group-containing side chains along a backbone forming the polymer, (ii) an antimicrobial agent selected from quaternary ammonium compounds, gentian violet compounds, substituted or unsubstituted phenols, biguanide compounds, iodine compounds, and mixtures thereof, and (iii) a crosslinking agent containing functional groups capable of reacting with the amino groups. In one embodiment, the polymer is a polyamide formed from a maleic anhydride or maleic acid ester monomer and alkylamines thereby producing a polyamide having amino substituted alkyl chains on one side of the polyamide backbone; the crosslinking agent is a phosphine having the general formula (A)3P wherein A is hydroxyalkyl; and the antimicrobial agent is chlorhexidine, dimethylchlorophenol, cetyl pyridinium chloride, gentian violet, triclosan, thymol, iodine, and mixtures thereof.

Semi-interpenetrating networks based on POLY(N-isopropyl acrilamide and POLY(N-vinylpyrrolidone

Directory of Open Access Journals (Sweden)

Žugić Dragana

2007-01-01

Full Text Available Three series of semi-interpenetrating polymer networks based on cross-linked poly(N-isopropylacrylamide, PNIPA, and 1, 2 and 3 wt% of linear poly(N-vinylpyrrolidone, PVP, were synthesized in order to improve the mechanical properties of PNIPA gels. The effect of the incorporation of the linear PVP polymer into the temperature responsive networks on the phase transition temperature, swelling behavior and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with various molar ratios (25/1 to 100/1 of the monomer (N-isopropylacrylamide to the cross linker (N,N'-methylene-bisacrylamide. The hydrogels were characterized by determination of the equilibrium degree of swelling at 25 °C, the dynamic shear modulus and the effective crosslinking density, as well as the ultimate hydrogel properties, such as the tensile strength and elongation at break. Furthermore, the deswelling kinetics of the hydrogels was also studied by measuring their water retention capacity. The inclusion of the linear hydrophilic PVP in the PNIPA networks increased the equilibrium degree of swelling, the highest values of which were obtained for samples with 2 and 3 wt% of PVP and the NIPA/MBA molar ratio of 75/1 and 100/1. The highest reinforcement effect, evaluated from the ratio of G'red(semi-IPN to G'red(PNIPA, was obtained by incorporation of 2 wt% PVP. The tensile strength of the semi-IPNs reinforced with linear PVP was higher than that of the PNIPA networks. The elongation at break of these semi-IPNs varied between 22 and 55%, which are 22^11% larger than those for single PNIPA networks. The tensile measurements confirmed that the presence of 2 wt% of the linear polymer significantly reinforced the PNIPA network.

Polycaprolactone diacrylate crosslinked biodegradable semi-interpenetrating networks of polyacrylamide and gelatin for controlled drug delivery

Energy Technology Data Exchange (ETDEWEB)

Jaiswal, Maneesh; Koul, Veena [Centre for Biomedical Engineering, Indian Institute of Technology, New Delhi 110016 (India); Dinda, Amit K [Department of Pathology, All India Institute of Medical Sciences, New Delhi 110029 (India); Gupta, Asheesh, E-mail: veenak_iitd@yahoo.co [Department of Biochemical Pharmacology, Defense Institute of Physiology and Allied Sciences, Ministry of Defense, New Delhi 110059 (India)

2010-12-15

A biodegradable semi-interpenetrating hydrogel network (semi-IPN) of polyacrylamide and gelatin was prepared using polycaprolactone diacrylate (mol. wt {approx} 640) as a crosslinker. The drug-polymer interaction and IPN formation were investigated by attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and thermal gravimetric analysis (TGA). Scanning electron micrographs of lyophilized matrices revealed porous internal structure with varying pore sizes under equilibrium hydrated conditions, depending upon formulation composition. pH-dependent swelling and degradation was enhanced with increasing gelatin content and decreasing crosslinker concentration (Cs). Compression modulus (CM) (at 20% strain) increased significantly from 23 {+-} 1.4 to 75 {+-} 2.7 kPa (p < 0.02) with increasing Cs (from 0.5 to 2.0 mol%), while it decreased from 162 {+-} 6.4 to 23 {+-} 1.4 kPa (p < 0.05) with decreasing PAm/G ratio. Cell viability studies by MTT assay showed excellent cytocompatibility of matrices with fibroblast L929 cells. Curcumin, a hydrophobic phytochemical, was loaded by a diffusion method and its release profile was investigated in 4% w/v aqueous BSA solution at 75 rpm (at 37 {+-} 0.2 {sup 0}C). Fitting of drug release data in the Korsmeyer-Peppas model suggested sustained release behavior up to 10 days with a combination of diffusion and erosion mechanism (0.5 < n < 1.0; M{sub t}/M{sub {infinity} {<=}} 0.6). The newly developed porous, biodegradable and elastic semi-IPNs may serve as an ideal matrix for controlled drug release and wound healing applications. The possibilities can be explored for pharmaceutical and tissue engineering applications.

Effect of crosslinking UHMWPE on its tensile and compressive creep performance.

Science.gov (United States)

Lewis, G; Carroll, M

2001-01-01

The in vitro quasi-static tensile and compressive creep properties of three sets of GUR 1050 ultra-high-molecular-weight polyethylene (UHMWPE) specimens were obtained. These sets were: control (as-received stock); "low-gamma" (specimens were crosslinked using gamma radiation, with a minimum dose of 5 Mrad); and "high-gamma" (specimens were crosslinked using gamma radiation, with a minimum dose of 15 Mrad). The % crystallinity (%C) and crosslink density (rho(x)) of the specimens in the three sets were also obtained. It was found that, in both tension and compression, crosslinking resulted in a significant depreciation in the creep properties, relative to control. The trend in the creep results is explained in terms of the impact of crosslinking on the polymer's %C and rho(x). The present results are in contrast to literature reports that show that crosslinking enhances the wear resistance of the polymer. The implications of the present results, taken together with the aforementioned literature results, are fully discussed vis-a-vis the use of crosslinked UHMWPE for fabricating articular components for arthroplasties.

Crosslinking of wire and cable insulation using electron accelerators

International Nuclear Information System (INIS)

Feng Yongxiang; Ma Zueteh

1992-01-01

Radiation crosslinking of wire and cable insulation is a well-established technology that is widely used in industry. The advantages of radiation crosslinking over chemical crosslinking have helped maintain its steady growth. Since successful utilization of electron beam processing relies on the formulation of compounds used in insulation, the radiation crosslinking of various polymers is reviewed. The handling technology for crosslinking wire and cable insulation and the throughput capacity of electron beam processors are also discussed. More than 30% of the industrial electron accelerators in the world are used for the radiation crosslinking of wire and cable insulation. Prospects of increased use of electron accelerators for crosslinking of wire and cable insulation are very good. (orig.)

Selective removal of heavy metal ions by disulfide linked polymer networks

DEFF Research Database (Denmark)

Ko, Dongah; Sung Lee, Joo; Patel, Hasmukh A.

2017-01-01

Heavy metal contaminated surface water is one of the oldest pollution problems, which is critical to ecosystems and human health. We devised disulfide linked polymer networks and employed as a sorbent for removing heavy metal ions from contaminated water. Although the polymer network material has...... a moderate surface area, it demonstrated cadmium removal efficiency equivalent to highly porous activated carbon while it showed 16 times faster sorption kinetics compared to activated carbon, owing to the high affinity of cadmium towards disulfide and thiol functionality in the polymer network. The metal...... sorption mechanism on polymer network was studied by sorption kinetics, effect of pH, and metal complexation. We observed that the metal ions―copper, cadmium, and zinc showed high binding affinity in polymer network, even in the presence of competing cations like calcium in water....

Hyaluronan microgel as a potential carrier for protein sustained delivery by tailoring the crosslink network

Energy Technology Data Exchange (ETDEWEB)

Luo, Chunhong [Department of Materials Science and Engineering, College of Science and Engineering, Jinan University, Guangzhou 510632 (China); Zhao, Jianhao, E-mail: jhzhao@jnu.edu.cn [Department of Materials Science and Engineering, College of Science and Engineering, Jinan University, Guangzhou 510632 (China); Engineering Research Center of Artificial Organs and Materials, Ministry of Education, Guangzhou 510632 (China); Tu, Mei; Zeng, Rong; Rong, Jianhua [Department of Materials Science and Engineering, College of Science and Engineering, Jinan University, Guangzhou 510632 (China); Engineering Research Center of Artificial Organs and Materials, Ministry of Education, Guangzhou 510632 (China)

2014-03-01

Hyaluronan (HA) microgels with different crosslink network, i.e. HGPs-1, HGPs-1.5, HGPs-3, HGPs-6 and HGPs-15, were synthesized using divinyl sulfone (DVS) as the crosslinker in an inverse microemulsion system for controlling the sustained delivery of bovine serum albumin (BSA). With increasing the crosslinker content, the average particle size slightly increased from 1.9 ± 0.3 μm to 3.6 ± 0.5 μm by dynamic laser scattering analysis. However, the crosslinker content had no significant effect on the morphology of HA microgels by scanning and transmission electron microscopes. Fourier transform infrared spectroscopy and elemental analysis proved more sulfur participated in the crosslink reaction when raising the crosslinker amount. The water swelling test confirmed the increasing crosslink density with the crosslinker content by calculating the average molecular weight between two crosslink points to be 8.25 ± 2.51 × 10{sup 5}, 1.26 ± 0.43 × 10{sup 5}, 0.96 ± 0.09 × 10{sup 5}, 0.64 ± 0.03 × 10{sup 5}, and 0.11 ± 0.01 × 10{sup 5} respectively. The degradation of HA microgels by hyaluronidase slowed down by enhancing the crosslink density, only about 5% of HGPs-15 was degraded as opposed to over 90% for HGPs-1. BSA loading had no obvious influence on the surface morphology of HA microgels but seemed to induce their aggregation. The increase of crosslink density decreased the BSA loading capacity but facilitated its long-term sustained delivery. When the molar ratio of DVS to repeating unit of HA reached 3 or higher, similar delivery profiles were obtained. Among all these HA microgels, HGPs-3 was the optimal carrier for BSA sustained delivery in this system because it possessed both high BSA loading capacity and long-term delivery profile simultaneously. - Highlights: • HA microgels with different crosslink densities were prepared. • The crosslinker content had little effect on the morphology and size of HA microgels. • The crosslink density

Thiolated and S-protected hydrophobically modified cross-linked poly(acrylic acid)--a new generation of multifunctional polymers.

Science.gov (United States)

Bonengel, Sonja; Haupstein, Sabine; Perera, Glen; Bernkop-Schnürch, Andreas

2014-10-01

The aim of this study was to create a novel multifunctional polymer by covalent attachment of l-cysteine to the polymeric backbone of hydrophobically modified cross-linked poly(acrylic acid) (AC1030). Secondly, the free thiol groups of the resulting thiomer were activated using 2-mercaptonicotinic acid (2-MNA) to provide full reactivity and stability. Within this study, 1167.36 μmol cysteine and 865.72 μmol 2-MNA could be coupled per gram polymer. Studies evaluating mucoadhesive properties revealed a 4-fold extended adherence time to native small intestinal mucosa for the thiomer (AC1030-cysteine) as well as an 18-fold prolonged adhesion for the preactivated thiomer (AC1030-Cyst-2-MNA) compared to the unmodified polymer. Modification of the polymer led to a higher tablet stability concerning the thiomer and the S-protected thiomer, but a decelerated water uptake could be observed only for the preactivated thiomer. Neither the novel conjugates nor the unmodified polymer showed severe toxicity on Caco-2 cells. Evaluation of emulsification capacity proofed the ability to incorporate lipophilic compounds like medium chain triglycerides and the preservation of the emulsifying properties after the modifications. According to these results thiolated AC1030 as well as the S-protected thiolated polymer might provide a promising tool for solid and semisolid formulations in pharmaceutical development. Copyright © 2014 Elsevier B.V. All rights reserved.

Crosslinked anion exchange membranes with primary diamine-based crosslinkers for vanadium redox flow battery application

Science.gov (United States)

Cha, Min Suc; Jeong, Hwan Yeop; Shin, Hee Young; Hong, Soo Hyun; Kim, Tae-Ho; Oh, Seong-Geun; Lee, Jang Yong; Hong, Young Taik

2017-09-01

A series of polysulfone-based crosslinked anion exchange membranes (AEMs) with primary diamine-based crosslinkers has been prepared via simple a crosslinking process as low-cost and durable membranes for vanadium redox flow batteries (VRFBs). Chloromethylated polysulfone is used as a precursor polymer for crosslinked AEMs (CAPSU-x) with different degrees of crosslinking. Among the developed AEMs, CAPSU-2.5 shows outstanding dimensional stability and anion (Cl-, SO42-, and OH-) conductivity. Moreover, CAPSU-2.5 exhibits much lower vanadium ion permeability (2.72 × 10-8 cm2 min-1) than Nafion 115 (2.88 × 10-6 cm2 min-1), which results in an excellent coulombic efficiency of 100%. The chemical and operational stabilities of the membranes have been investigated via ex situ soaking tests in 0.1 M VO2+ solution and in situ operation tests for 100 cycles, respectively. The excellent chemical, physical, and electrochemical properties of the CAPSU-2.5 membrane make it suitable for use in VRFBs.

Understanding interpenetrating-polymer-network-like porous nitrile butadiene rubber hybrids by their long-period miscibility

International Nuclear Information System (INIS)

Zhang, Jihua; Wang, Lifeng; Zhao, Yunfeng

2013-01-01

Highlights: • Hydrogen bonds are introduced into NBR to develop its IPN-like porous hybrids. • NBR is partly miscible with AO-60. • AO-60 possesses the viscoelastic behavior resembling that of polymers. • Phase separation aggravates and AO-60 crystallizes in the durations. • The porous hybrids may have potential damping applications. - Abstract: In this article, tetrakis [methylene-3-(3, 5-di-tert-butyl-4-hydroxy phenyl) propionyloxy] methane (AO-60) with hydrogen bonds was designed to interpenetrate into the chemical crosslinking bonds of nitrile butadiene rubber (NBR) and then porous materials were prepared. Scanning electron microscopy (SEM), atomic force microscopy (AFM) images and dynamic mechanical analyses (DMA) demonstrate that NBR is partly miscible with AO-60 which induces the micro-pores and interpenetrating-polymer-network (IPN)-like phase morphology in the hybrids. The wide double tan δ peak in DMA curve displays that AO-60 possesses similar viscoelastic behaviors to polymers which come from supramolecular interactions between polar groups of NBR chains and hydroxyl (OH) groups of AO-60. To further understand the supramolecular abilities of AO-60 in the rubber, the long-period observations for their miscibility are conducted. With the increase of durations, the hydrogen bond network from AO-60 is weakened. The phase separation between AO-60 and NBR is aggravated and even extremely few AO-60 crystallizes which develops multi-scale porous morphology in the hybrids. It is believed that these findings can serve as a guide for the designs of the IPN-like hybrids with small molecule substances and their applications of damping materials

Synthesis of Hydrophobic, Crosslinkable Resins.

Science.gov (United States)

1985-12-01

product by methanol precipitation the majority of the first oligomer was L-"- lost. 4.14 DIFFERENTIAL SCANNING CALORIMETRY. The DSC trace of a typical...polymer from the DSC traces obtained to dcte. Preliminary studies using an automated torsional pendulum indicate that the Tg of the crosslinked polymer is...enabling water to be used in the purification steps. The diethyl phosphonates are readily prepared by heating triethyl phosphite with the chloromethyl

Polymerization speed and diffractive experiments in polymer network LC test cells

Science.gov (United States)

Braun, Larissa; Gong, Zhen; Habibpourmoghadam, Atefeh; Schafforz, Samuel L.; Wolfram, Lukas; Lorenz, Alexander

2018-02-01

Polymer-network liquid crystals (LCs), where the response properties of a LC can be enhanced by the presence of a porous polymer network, are investigated. In the reported experiments, liquid crystals were doped with a small amount (situ generated polymer network, the electro-optic response properties of photo cured samples were enhanced. For example, their continuous phase modulation properties led to more localized responses in samples with interdigitated electrodes, which caused suppression of selected diffraction orders in the diffraction patterns recorded in polymer network LC samples. Moreover, capacitance changes were investigated during photopolymerization of a blue phase LC.

Polymeric molecular sieve membranes via in situ cross-linking of non-porous polymer membrane templates.

Science.gov (United States)

Qiao, Zhen-An; Chai, Song-Hai; Nelson, Kimberly; Bi, Zhonghe; Chen, Jihua; Mahurin, Shannon M; Zhu, Xiang; Dai, Sheng

2014-04-16

High-performance polymeric membranes for gas separation are attractive for molecular-level separations in industrial-scale chemical, energy and environmental processes. Molecular sieving materials are widely regarded as the next-generation membranes to simultaneously achieve high permeability and selectivity. However, most polymeric molecular sieve membranes are based on a few solution-processable polymers such as polymers of intrinsic microporosity. Here we report an in situ cross-linking strategy for the preparation of polymeric molecular sieve membranes with hierarchical and tailorable porosity. These membranes demonstrate exceptional performance as molecular sieves with high gas permeabilities and selectivities for smaller gas molecules, such as carbon dioxide and oxygen, over larger molecules such as nitrogen. Hence, these membranes have potential for large-scale gas separations of commercial and environmental relevance. Moreover, this strategy could provide a possible alternative to 'classical' methods for the preparation of porous membranes and, in some cases, the only viable synthetic route towards certain membranes.

Self-reinforcement and protein sustained delivery of hyaluronan hydrogel by tailoring a dually cross-linked network

Energy Technology Data Exchange (ETDEWEB)

Luo, Chunhong; Xu, Guoguang; Wang, Xinghui [Department of Materials Science and Engineering, College of Science and Engineering, Jinan University, Guangzhou 510632 (China); Tu, Mei; Zeng, Rong; Rong, Jianhua [Department of Materials Science and Engineering, College of Science and Engineering, Jinan University, Guangzhou 510632 (China); Engineering Research Center of Artificial Organs and Materials, Ministry of Education, Guangzhou 510632 (China); Zhao, Jianhao, E-mail: jhzhao@jnu.edu.cn [Department of Materials Science and Engineering, College of Science and Engineering, Jinan University, Guangzhou 510632 (China); Engineering Research Center of Artificial Organs and Materials, Ministry of Education, Guangzhou 510632 (China)

2015-01-01

A series of self-reinforcing hyaluronan hydrogels were developed to improve mechanical properties and protein sustained delivery thanks to a dually cross-linked network. Hyaluronan gel particles (HGPs, 1–5 μm in diameter) with different cross-linking densities, i.e. HGPs-1.5, HGPs-3 and HGPs-15, were prepared in an inverse emulsion system and used as the reinforcing phase after glycidyl methacrylation, while glycidyl methacrylated hyaluronan with a substitution degree of 45.2% was synthesized as the matrix phase. These two phases were cross-linked under ultraviolet irradiation to form self-reinforcing hyaluronan hydrogels (srHAs) that showed typical cross-linked structure of HGPs connecting the matrix phase by cross-section observation. In comparison to hyaluronan bulk gels and their blends with HGPs, srHAs distinctly enhanced the mechanical properties and BSA long-term sustained delivery, especially srHA-1.5 showed the highest compressive modulus of 220 ± 15 kPa and the slowest BSA delivery (67% release at 14 d). The 3T3 fibroblast cell culture showed that all the srHAs had no cytotoxicity. - Highlights: • New self-reinforcing HA hydrogels with a dually cross-linked network were developed. • Self-reinforcing HA hydrogels greatly enhanced the mechanical properties. • Self-reinforcing HA hydrogels prolonged the sustained delivery of BSA. • The self-reinforcing mechanism and BSA diffusion mechanism were discussed. • Self-reinforcing HA hydrogels had no cytotoxicity to 3T3 fibroblast cells.

Self-reinforcement and protein sustained delivery of hyaluronan hydrogel by tailoring a dually cross-linked network

International Nuclear Information System (INIS)

Luo, Chunhong; Xu, Guoguang; Wang, Xinghui; Tu, Mei; Zeng, Rong; Rong, Jianhua; Zhao, Jianhao

2015-01-01

A series of self-reinforcing hyaluronan hydrogels were developed to improve mechanical properties and protein sustained delivery thanks to a dually cross-linked network. Hyaluronan gel particles (HGPs, 1–5 μm in diameter) with different cross-linking densities, i.e. HGPs-1.5, HGPs-3 and HGPs-15, were prepared in an inverse emulsion system and used as the reinforcing phase after glycidyl methacrylation, while glycidyl methacrylated hyaluronan with a substitution degree of 45.2% was synthesized as the matrix phase. These two phases were cross-linked under ultraviolet irradiation to form self-reinforcing hyaluronan hydrogels (srHAs) that showed typical cross-linked structure of HGPs connecting the matrix phase by cross-section observation. In comparison to hyaluronan bulk gels and their blends with HGPs, srHAs distinctly enhanced the mechanical properties and BSA long-term sustained delivery, especially srHA-1.5 showed the highest compressive modulus of 220 ± 15 kPa and the slowest BSA delivery (67% release at 14 d). The 3T3 fibroblast cell culture showed that all the srHAs had no cytotoxicity. - Highlights: • New self-reinforcing HA hydrogels with a dually cross-linked network were developed. • Self-reinforcing HA hydrogels greatly enhanced the mechanical properties. • Self-reinforcing HA hydrogels prolonged the sustained delivery of BSA. • The self-reinforcing mechanism and BSA diffusion mechanism were discussed. • Self-reinforcing HA hydrogels had no cytotoxicity to 3T3 fibroblast cells

An all-aromatic polypyridine: Monomer and polymer synthesis; Film formation and crosslinking; A candidate fuel cell membrane

Science.gov (United States)

Sikkema, Doetze J.; Versteegen, Ron M.; Pouderoijen, Maarten J.; Janssen, Henk M.; Boere, Ben; Brands, Ferry; Kemperman, GerJan; Rewinkel, Jos B. M.; Koeman, Menno

2018-03-01

2,6-di (3-pyridyl)phenol and the title polymer are synthesized at 1 kg scale. Polymer is processed and crosslinked without the introduction of non-aromatic moieties after shaping into membranes. Attractive proton conduction, at high temperature (140-180 °C: 300 mS cm-1) and at room temperature (60 mS cm-1) are recorded in the dry state (higher numbers at modest humidity) and excellent retention of properties after challenge by humidity (in contrast with state-of-the-art PBI membranes). Functional fuel cells are made and tested. In prolonged use the membrane is plasticized and this seems attributable to curing reversal at the hydrogen electrode. For high temperature fuel cell use, another curing scheme (again without the introduction of aliphatic character) must be found.

A preliminary assessment of the effects of radiation on polymer properties

International Nuclear Information System (INIS)

Dickson, L.W.

1988-01-01

The literature on the effects of radiation on the properties of various polymers and composites has been briefly reviewed for the purpose of identifying polymeric materials that could be irradiated to improve their performance. Radiation treatment of polymers may lead to cross-linking or chain scission reactions, depending on the chemical nature of the polymer. Cross-linking generally leads to an improvement in the mechanical properties of the polymer. Chain scission leads to deterioration in mechanical properties. The properties of irradiated polymers also depend on the degree of polymer crystallinity and the irradiation conditions, including dose rate and the presence of oxygen, cross-linking agents and other additives. A 30% increase in the tensile strength of many polymers may be obtained by radiation cross-linking under appropriate conditions. 40 refs

Molecular dynamics modeling of polymer flammability

International Nuclear Information System (INIS)

Nyden, M.R.; Brown, J.E.; Lomakin, S.M.

1992-01-01

Molecular dynamic simulations were used to identify factors which promote char formation during the thermal degradation of polymers. Computer movies based on these simulations, indicate that cross-linked model polymers tend to undergo further cross-linking when burned, eventually forming a high molecular weight, thermally stable char. This paper reports that the prediction was confirmed by char yield measurements made on γ and e - -irradiated polyethylene and chemically cross-linked poly(methyl methacrylate)

Bimodal Networks as Candidates for Electroactive Polymers

DEFF Research Database (Denmark)

Bahrt, Frederikke; Daugaard, Anders Egede; Bejenariu, Anca Gabriela

An alternative network formulation method was adopted in order to obtain a different type of silicone based elastomeric systems - the so-called bimodal networks - using two vinyl-terminated polydimethyl siloxanes (PDMS) of different molecular weight, a labelled crosslinker (3 or 4-functional), an...... themselves between the long chains and show how this leads to unexpectedly good properties for DEAP purposes due both to the low extensibility of the short chains that attach strongly the long chains and to the extensibility of the last ones that retards the rupture process....

Effects of Supercritical CO 2 Conditioning on Cross-Linked Polyimide Membranes

KAUST Repository

Kratochvil, Adam M.; Koros, William J.

2010-01-01

The effects of supercritical CO2 (scCO2) conditioning on high-performance cross-linked polyimide membranes is examined through gas permeation and sorption experiments. Under supercritical conditions, the cross-linked polymers do not exhibit a

Polymer and Polymer Gel of Liquid Crystalline Semiconductors

Institute of Scientific and Technical Information of China (English)

Teppei Shimakawa; Naoki Yoshimoto; Jun-ichi Hanna

2004-01-01

It prepared a polymer and polymer gel of a liquid crystalline (LC) semiconductor having a 2-phenylnaphthalene moiety and studied their charge carrier transport properties by the time-of-flight technique. It is found that polyacrylate having the mesogenic core moiety of 2-phenylnaphtalene (PNP-acrylate) exhibited a comparable mobility of 10-4cm2/Vs in smectic A phase to those in smectic A (SmA) phase of small molecular liquid crystals with the same core moiety, e.g., 6-(4'-octylphenyl)- 2-dodecyloxynaphthalene (8-PNP-O12), and an enhanced mobility up to 10-3cm2/Vs in the LC-glassy phase at room temperature, when mixed with a small amount of 8-PNP-O12. On the other hand, the polymer gel consisting of 20 wt %-hexamethylenediacrylate (HDA)-based cross-linked polymer and 8-PNP-O12 exhibited no degraded mobility when cross-linked at the mesophase. These results indicate that the polymer and polymer composite of liquid crystalline semiconductors provide us with an easy way to realize a quality organic semiconductor thin film for the immediate device applications.

Flexible, elastic and tear-resistant networks prepared by photo-crosslinking poly(trimethylene carbonate) macromers

NARCIS (Netherlands)

Schuller-Ravoo, S.; Feijen, J.; Grijpma, D. W.

2012-01-01

Poly(trimethylene carbonate) (PTMC) macromers with molecular weights (M-n) between 1000 and 41,000 g mol(-1) were prepared by ring opening polymerization and subsequent functionalization with methacrylate end groups. Flexible networks were obtained by radical photo-crosslinking reactions of these

A zwitterionic macro-crosslinker for durable non-fouling coatings.

Science.gov (United States)

Wang, Wei; Lu, Yang; Xie, Jinbing; Zhu, Hui; Cao, Zhiqiang

2016-03-28

A novel zwitterionic macro-crosslinker was developed and applied to fabricate durable non-fouling coatings on a polyurethane substrate. The zwitterionic macro-crosslinker coating exhibited superior durability over the traditional brush polymer coating and was able to retain its non-fouling property even after weeks of shearing in flowing liquid.

Sequential optimization of methotrexate encapsulation in micellar nano-networks of polyethyleneimine ionomer containing redox-sensitive cross-links.

Science.gov (United States)

Abolmaali, Samira Sadat; Tamaddon, Ali; Yousefi, Gholamhossein; Javidnia, Katayoun; Dinarvand, Rasoul

2014-01-01

A functional polycation nanonetwork was developed for delivery of water soluble chemotherapeutic agents. The complexes of polyethyleneimine grafted methoxy polyethylene glycol (PEI-g-mPEG) and Zn(2+) were utilized as the micellar template for cross-linking with dithiodipropionic acid, followed by an acidic pH dialysis to remove the metal ion from the micellar template. The synthesis method was optimized according to pH, the molar ratio of Zn(2+), and the cross-link ratio. The atomic force microscopy showed soft, discrete, and uniform nano-networks. They were sensitive to the simulated reductive environment as determined by Ellman's assay. They showed few positive ζ potential and an average hydrodynamic diameter of 162±10 nm, which decreased to 49±11 nm upon dehydration. The ionic character of the nano-networks allowed the achievement of a higher-loading capacity of methotrexate (MTX), approximately 57% weight per weight, depending on the cross-link and the drug feed ratios. The nano-networks actively loaded with MTX presented some suitable properties, such as the hydrodynamic size of 117±16 nm, polydispersity index of 0.22, and a prolonged swelling-controlled release profile over 24 hours that boosted following reductive activation of the nanonetwork biodegradation. Unlike the PEI ionomer, the nano-networks provided an acceptable cytotoxicity profile. The drug-loaded nano-networks exhibited more specific cytotoxicity against human hepatocellular carcinoma cells if compared to free MTX at concentrations above 1 μM. The enhanced antitumor activity in vitro might be attributed to endocytic entry of MTX-loaded nano-networks that was found in the epifluorescence microscopy experiment for the fluorophore-labeled nano-networks.

Stabilized Sulfonated Aromatic Polymers by in situ Solvothermal Cross-Linking

Energy Technology Data Exchange (ETDEWEB)

Di Vona, Maria Luisa, E-mail: divona@uniroma2.it; Sgreccia, Emanuela [Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, Rome (Italy); Narducci, Riccardo; Pasquini, Luca [Dipartimento di Scienze e Tecnologie Chimiche, Università di Roma Tor Vergata, Rome (Italy); MAtériaux Divisés, Interfaces, Réactivité, ELectrochimie (MADIREL – UMR 7246), Aix Marseille Université, Marseille (France); Hou, Hongying [Faculty of Material and Engineering, Kunming University of Science and Technology, Kunming (China); Knauth, Philippe [MAtériaux Divisés, Interfaces, Réactivité, ELectrochimie (MADIREL – UMR 7246), Aix Marseille Université, Marseille (France)

2014-10-10

The cross-link reaction via sulfone bridges of sulfonated polyether ether ketone (SPEEK) by thermal treatment at 180°C in presence of dimethylsulfoxide is discussed. The modifications of properties subsequent to the cross-linking are presented. The mechanical strength as well as the hydrolytic stability increased with the thermal treatment time, i.e., with the degree of cross-linking. The proton conductivity was determined as function of temperature, IEC, degree of cross-linking, and hydration number. The memory effect, which is the membrane ability to “remember” the water uptake reached at high temperature also at lower temperature, is exploited in order to achieve high values of conductivity. Membranes swelled at 110°C can reach a conductivity of 0.14 S/cm at 80°C with a hydration number (λ) of 73.

Introduction to radiation chemistry of polymer

Energy Technology Data Exchange (ETDEWEB)

Mohd Dahlan, Khairul Zaman [Nuclear Energy Unit, Bangi, Selangor (Malaysia)

1994-12-31

The topics briefly discussed are 1. What are radiation chemistry 2. Type of ionising radiation 3. gamma rays versus electron beam 4. Interaction of radiation with matters 5. What is polymers 6. Techniques of crosslinking 7. Crosslinking of polymers i.e. polyethylene, ethylene copolymer, polypropylene, polyamides, polyvinyl chloride, natural rubber.

Introduction to radiation chemistry of polymer

International Nuclear Information System (INIS)

Khairul Zaman Mohd Dahlan

1994-01-01

The topics briefly discussed are 1. What are radiation chemistry 2. Type of ionising radiation 3. gamma rays versus electron beam 4. Interaction of radiation with matters 5. What is polymers 6. Techniques of crosslinking 7. Crosslinking of polymers i.e. polyethylene, ethylene copolymer, polypropylene, polyamides, polyvinyl chloride, natural rubber

Temperature dependence of deformation vs. strength properties of radiation-crosslinked polyethylene

International Nuclear Information System (INIS)

Matusevich, Yu.I.; Krul', L.P.

1992-01-01

The authors have studied the deformation vs. strength properties of radiation-crosslinked low-density polyethylene irradiated by γ irradiation up to doses from 5.0 sm-bullet 10 4 to 1.0 sm-bullet 10 6 Gy. The authors present the elongation diagrams taken at temperatures below and above the melting point of the polymer. The authors have obtained the dependences of the breaking stress and the pre-break elongation of the polymer on the irradiation doses and the testing temperature. Based on the kinetic lifetime equation, The authors calculated the values of the activation energy for mechanical fracture and the structure-sensitive coefficient γ. The authors show that in the crystalline state the strength of radiation-crosslinked polyethylene is determined by the chemical interactions along the chain of polymer macromolecules; and in molten polyethylene, by the crosslinks between the macromolecules. 8 refs., 4 figs., 1 tab

Studies on radiation stability of polymers

International Nuclear Information System (INIS)

Jiazhen Sun; Xiaoguang Zhong

1999-01-01

Fluoropolyimide (FPI) is crosslinked by gamma-irradiation at high temperature. After crosslinking, the glass transition temperature is increased with increasing dose. High temperature tensile strength is also increased with increasing dose. The high temperature water resistance property is improved markedly. XPS results show that the fluoro-atom in the CF 3 group is decreased during radiation crosslinking of PFI, so the crosslinking reaction of PFI is thought to proceed through defluorination. Likewise, certain common polyolefins, such as polytetrafluoroethylene, which undergo primarily chain scission when irradiated at room temperature, can be crosslinked by irradiation at high temperature. This dramatically improves their subsequent radiation resistance. We have also been able to achieve improved radiation resistance by irradiation of certain blends of a predominantly scissioning polymer with a predominantly crosslinking polymer. (author)

Swelling of radiation crosslinked acrylamide-based microgels and their potential applications

Energy Technology Data Exchange (ETDEWEB)

Abd El-Rehim, H.A. [National Center for Radiation Research and Technology, Atomic Energy Authority, P.O. Box 29 Nasr City, Cairo (Egypt)]. E-mail: ha_rehim@hotmail.com

2005-10-01

Crosslinked polyacrylamide PAAm and acrylamide-Na-acrylate P(AAm-Na-AAc) microgels were prepared by electron beam irradiation. It was found that the dose required for crosslinking depends on the polymer moisture content, so that the dose to obtain PAAm of maximum gel fraction was over 40 and 20 kGy for dry and moist PAAm, respectively. The structural changes in irradiated PAAm were investigated using FTIR and SEM. The swelling property of such microgels in distilled water and real urine solution was determined and crosslinked polymers reached their equilibrium swelling state in a few minutes. As the gel content and crosslinking density decrease, the swelling of the microgels increases. The ability of the microgels to absorb and retain large amount of solutions suggested their possible uses in horticulture and in hygienic products such as disposable diapers.

Swelling of radiation crosslinked acrylamide-based microgels and their potential applications

International Nuclear Information System (INIS)

Abd El-Rehim, H.A.

2005-01-01

Crosslinked polyacrylamide PAAm and acrylamide-Na-acrylate P(AAm-Na-AAc) microgels were prepared by electron beam irradiation. It was found that the dose required for crosslinking depends on the polymer moisture content, so that the dose to obtain PAAm of maximum gel fraction was over 40 and 20 kGy for dry and moist PAAm, respectively. The structural changes in irradiated PAAm were investigated using FTIR and SEM. The swelling property of such microgels in distilled water and real urine solution was determined and crosslinked polymers reached their equilibrium swelling state in a few minutes. As the gel content and crosslinking density decrease, the swelling of the microgels increases. The ability of the microgels to absorb and retain large amount of solutions suggested their possible uses in horticulture and in hygienic products such as disposable diapers

Method of cross-linking polyvinyl alcohol and other water soluble resins

Science.gov (United States)

Phillipp, W. H.; May, C. E.; Hsu, L. C.; Sheibley, D. W. (Inventor)

1980-01-01

A self supporting sheet structure comprising a water soluble, noncrosslinked polymer such as polyvinyl alcohol which is capable of being crosslinked by reaction with hydrogen atom radicals and hydroxyl molecule radicals is contacted with an aqueous solution having a pH of less than 8 and containing a dissolved salt in an amount sufficient to prevent substantial dissolution of the noncrosslinked polymer in the aqueous solution. The aqueous solution is then irradiated with ionizing radiation to form hydrogen atom radicals and hydroxyl molecule radicals and the irradiation is continued for a time sufficient to effect crosslinking of the water soluble polymer to produce a water insoluble polymer sheet structure. The method has particular application in the production of battery separators and electrode envelopes for alkaline batteries.

Porous polymer networks and ion-exchange media and metal-polymer composites made therefrom

Energy Technology Data Exchange (ETDEWEB)

Kanatzidis, Mercouri G.; Katsoulidis, Alexandros

2016-10-18

Porous polymeric networks and composite materials comprising metal nanoparticles distributed in the polymeric networks are provided. Also provided are methods for using the polymeric networks and the composite materials in liquid- and vapor-phase waste remediation applications. The porous polymeric networks, are highly porous, three-dimensional structures characterized by high surface areas. The polymeric networks comprise polymers polymerized from aldehydes and phenolic molecules.

Stabilized sulfonated aromatic polymers by in situ solvothermal cross-linking

Directory of Open Access Journals (Sweden)

Maria Luisa eDi Vona

2014-10-01

Full Text Available The cross-link reaction via sulfone bridges of sulfonated polyetheretherketone (SPEEK by thermal treatment at 180 °C in presence of dimethylsulfoxide (DMSO is discussed. The modifications of properties subsequent to the cross-linking are presented. The mechanical strength as well as the hydrolytic stability increased with the thermal treatment time, i.e., with the degree of cross-linking. The proton conductivity was determined as function of temperature, IEC, degree of cross-linking and hydration number. The memory effect, which is the membrane ability to remember the water uptake reached at high temperature also at lower temperature, is exploited in order to achieve high values of conductivity. Membranes swelled at 110 °C can reach a conductivity of 0.14 S/cm at 80°C with a hydration number ( of 73.

Ecological concepts in recent polymer technology. Part4. Eco-friendly water-absorbing polymer; Kankyo ni chowa shita kyusuisei kobunshi

Energy Technology Data Exchange (ETDEWEB)

Kunioka, M.

1997-07-01

As an application example of water-absorbing polymers with biodegradability, it was expected to be applied to soil improvement agents used in planting trees in deserts, besides physiological napkins, paper diapers and medical materials. In this paper, water-absorbing polymers with biodegradability such as natural polymers, petroleum-made polymers and polymers synthesized by radiation cross-linking and chemical cross-linking were introduced. Moreover, a kind of water-absorbing polymers developed by the authors, made from polyamino acid synthesized by microbes, was introduced. In the method developed by the authors, the cross-linking structure could be made by combining PGA carboxyl groups and various amino groups of diamine using carbimide with water solubility. As for this method, all of reactions could be conducted in water and catalytic replacement was not necessary, moreover, hydrogel with the water-absorbing rate of 200 to 1500 times could be produced. 44 refs., 3 figs., 1 tab.

Effect of salt species on electrochemical properties of gel-type polymer electrolyte based on chemically crosslinking rubber

Energy Technology Data Exchange (ETDEWEB)

Lee, Kab Youl; Jo, Nam Ju [Pusan National Univ., Busan (Korea). Dept. of Polymer Science and Engineering; Chung, Won Sub [Pusan National Univ., Busan (Korea). School of Materials Science and Engineering

2004-11-30

In our study, for ion-polymer interaction in gel-type polymer electrolyte (GPE), two kinds of ions were used. GPE systems were composed of Mg or Li salt, organic solvent ({gamma}-BL), and polymer matrix prepared by chemical crosslinking of NBR with poly(ethylene glycol) methylethermethacrylate (PEGMEM) having polar group (--CH{sub 2}--CH{sub 2}--O--) in the side chain of monomer. GPE consisting of Li{sup +} ion had higher ionic conductivity than that of Mg{sup 2+} ion at below 100 wt.% of electrolyte content (1 M salt/{gamma}-BL). On the other hand, GPE consisting of Mg{sup 2+} ion had higher ionic conductivity than that consisting of Li{sup +} ion at over 120 wt.% of electrolyte content (1 M salt/{gamma}-BL). The maximum liquid electrolyte content was 200 wt.% for all GPE systems. And the highest ionic conductivity of 3.3 x 10{sup -2} S cm{sup -1} was achieved for the case of Mg{sup 2+}-GPE with 200 wt.% of liquid electrolyte contents at 20 C. The interaction between ionic species and polymer matrix in GPE was investigated by using Fourier transform infrared spectroscopy (FT-IR). Also, cyclic voltammogram of Mg{sup 2+}-GPE confirmed the electrochemical property of divalent cation with two electron-transfer reactions.

Radiation crosslinked block copolymer blends with improved impact resistance

International Nuclear Information System (INIS)

Saunders, F.L.; Pelletier, R.R.

1976-01-01

Polymer blends having high impact resistance after mechanical working are produced by blending together a non-elastomeric monovinylidene aromatic polymer such as polystyrene with an elastomeric copolymer, such as a block copolymer of styrene and butadiene, in the form of crosslinked, colloidal size particles

Chitosan–Collagen Coated Magnetic Nanoparticles for Lipase Immobilization—New Type of “Enzyme Friendly” Polymer Shell Crosslinking with Squaric Acid

Directory of Open Access Journals (Sweden)

Marta Ziegler-Borowska

2017-01-01

Full Text Available This article presents a novel route for crosslinking a polysaccharide and polysaccharide/protein shell coated on magnetic nanoparticles (MNPs surface via condensation reaction with squaric acid (SqA. The syntheses of four new types of collagen-, chitosan-, and chitosan–collagen coated magnetic nanoparticles as supports for enzyme immobilization have been done. Structure and morphology of prepared new materials were characterized by attenuated total reflectance Fourier-transform infrared (ATR-FTIR, XRD, and TEM analysis. Next, the immobilization of lipase from Candida rugosa was performed on the nanoparticles surface via N-(3-dimethylaminopropyl-N′-ethylcarbodiimide hydrochloride (EDC/N-hydroxy-succinimide (NHS mechanism. The best results of lipase activity recovery and specific activities were observed for nanoparticles with polymer shell crosslinked via a novel procedure with squaric acid. The specific activity for lipase immobilized on materials crosslinked with SqA (52 U/mg lipase was about 2-fold higher than for enzyme immobilized on MNPs with glutaraldehyde addition (26 U/mg lipase. Moreover, a little hyperactivation of lipase immobilized on nanoparticles with SqA was observed (104% and 112%.

Templating Organosilicate Vitrification Using Unimolecular Self Organizing Polymers: Evolution of Morphology and Nanoporosity Development with Network Formation

International Nuclear Information System (INIS)

Kim, H.-C.

2004-01-01

Star-shaped polymers with a compatibilizing outer corona were dispersed into a thermosetting organosilicate matrix and used to create a nanoporous material. These environmentally responsive copolymers create nano-sized domains through a matrix-mediated collapse of the interior core of the core-corona polymeric structure. This approach relies on the outer corona of the star to compatibilize the insoluble core with the thermosetting resin and prevent aggregation such that these individual molecules template the crosslinking of the matrix and ultimately generate a single hole. The organic polymer was selectively thermalized leaving behind its latent image in the matrix with a pore size that reflected the size of the polymer molecule, and provided the expected reduction in dielectric constant. The morphology development as a function of arm number, molecular weight and volume fraction in mixtures with organosilicates as a function of cure/network conversion was investigated by SAXS, SANS, DMA, TEM and FE-SEM measurements. Amphiphilic star-shaped polymers of various block lengths and arm number, prepared by tandem controlled ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP) from dendritic initiators, were further tailored to facilitate contrast enhancement for various measurements by the incorporation of either ferrocenyl units or deuterated monomers. The pore sizes achieved by the star and dendrimer-like star macromolecular architectures range from ∼7 to 40nm, depending on the molecular weight and architecture

Conditional repair by locally switching the thermal healing capability of dynamic covalent polymers with light

Science.gov (United States)

Fuhrmann, Anne; Göstl, Robert; Wendt, Robert; Kötteritzsch, Julia; Hager, Martin D.; Schubert, Ulrich S.; Brademann-Jock, Kerstin; Thünemann, Andreas F.; Nöchel, Ulrich; Behl, Marc; Hecht, Stefan

2016-12-01

Healable materials could play an important role in reducing the environmental footprint of our modern technological society through extending the life cycles of consumer products and constructions. However, as most healing processes are carried out by heat alone, the ability to heal damage generally kills the parent material's thermal and mechanical properties. Here we present a dynamic covalent polymer network whose thermal healing ability can be switched `on' and `off' on demand by light, thereby providing local control over repair while retaining the advantageous macroscopic properties of static polymer networks. We employ a photoswitchable furan-based crosslinker, which reacts with short and mobile maleimide-substituted poly(lauryl methacrylate) chains forming strong covalent bonds while simultaneously allowing the reversible, spatiotemporally resolved control over thermally induced de- and re-crosslinking. We reason that our system can be adapted to more complex materials and has the potential to impact applications in responsive coatings, photolithography and microfabrication.

A NOVEL APPROACH TO SYNTHESIZE CHITOSAN BEADS CROSSLINKED BY EPICHLOROHYDRIN

Institute of Scientific and Technical Information of China (English)

WANG Yongjian; BAI Shu; SUN Yan

2001-01-01

The present investigation describes a novel method for preparing spherical chitosan particles based on crosslinking with epichlorohydrin. Certain amount of pre-crosslinking agent was added to form chitosan gels by traditional inverse phase suspension polymerization. Then the gels were crosslinked by epichlorohydrin at basic condition to obtain chitosan beads. The effects of reaction conditions, such as crosslinking time, the amount of crosslinking agent and the NaOtt concentration,on the physical properties of the chitosan beads were investigated. The beads were found to have more amino groups in the polymer chains than the beads crosslinked by glutaraldehyde. The capacity for copper ions is as high as 40mg/g. The beads have good mechanical strength and can be reused.

A NOVEL APPROACH TO SYNTHESIZE CHITOSAN BEADS CROSSLINKED BY EPICHLOROHYDRIN

Institute of Scientific and Technical Information of China (English)

WANGYongjina; BAIShu; 等

2001-01-01

The present investigation describes a novel method for preparing spherical chitosan particles based on crosslinking with epichlorohydrin.Certain amount of pre-crosslinking agent was added to form chitosan gels by traditional inverse phase suspension polymerization.Then the gels were crosslinked by epichlorohydrin at basic condition to obtain chitosan beads.The effects of reaction conditions,such as crosslinking time,the amount of crosslinking agent and the NaOH concentration,on the physical properties of the chitosan beads were investigated.The beads were found to have more amino groups in the polymer chains than the beads crosslinked by glutaraldehyde.The capacity for copper ions in as high as 40mg/g,The beads have good mechanical strength and can be reused.

Comparison of neat and photo-crosslinked polyvinylidene fluoride-co-hexafluoropropylene thin film dielectrics formed by spin-coating

International Nuclear Information System (INIS)

Iyore, O.D.; Roodenko, K.; Winkler, P.S.; Noriega, J.R.; Vasselli, J.J.; Chabal, Y.J.; Gnade, B.E.

2013-01-01

We report the characterization of photo-crosslinked polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) thin film, metal–insulator–metal capacitors fabricated using standard semiconductor processing techniques. We characterize the capacitors using in-situ vibrational spectroscopy during thermally-assisted poling and correlate the Fourier transform infrared spectroscopy (FTIR) results with X-ray diffraction (XRD) results. FTIR analysis of the neat PVDF-HFP showed α → β transformations during poling at room temperature and at 55 °C. α → β transformations were observed for the crosslinked polymer only during poling at 55 °C. XRD data revealed that photo-crosslinking caused the polymer to partially crystallize into the β-phase. The similar behavior of the neat and crosslinked samples at 55 °C suggests that a higher activation energy was needed for α → β transformations in crosslinked PVDF-HFP during poling. Electrical measurements showed that photo-crosslinking had no significant effect on the dielectric constant and dielectric loss of PVDF-HFP. However, the dielectric strength and maximum energy density of the crosslinked polymer were severely reduced. - Highlights: • Polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) dielectrics were studied. • Phase transformations were observed only at 55 °C for the crosslinked PVDF-HFP. • Crosslinking had no strong effect on the dielectric constant of PVDF-HFP. • Breakdown strengths were 620 MVm −1 and 362 MVm −1 for neat and crosslinked films

Preparation of the Crosslinked Polyethersulfone Films by High Temperature Electron-Beam Irradiation

International Nuclear Information System (INIS)

Li, J.

2006-01-01

The aromatic polymers, mainly so called engineering plastics, were famed for the good stability under irradiation. However, high temperature irradiation of the aromatic polymers can result the crosslinked structure, due to the improved molecular mobility. Polyethersulfone (PES) is a wide used engineering plastic because of the high performance and high thermal stability. PES films were irradiated by electron-beam under nitrogen atmosphere above the glass transition temperature and then the covalently crosslinked PES (RX-PES) films were obtained. The irradiations were also performed at ambient temperature for comparison. The network structure formation of the RX-PES films was confirmed by the appearance of the gel, which were measured by soaking the irradiated PES films in the N,N-dimethylformamide (DMF) at room temperature. When the PES films were irradiated to 300 kGy, there was gel appeared. The gel percent increased with the increasing in the absorbed dose, and saturated when the absorbed dose exceeded 1200 kGy. However, there was no gel formed for the PES films irradiated at ambient temperature even to 2250 kGy. The G(S) and G(X) were calculated according to the Y-crosslinking mechanism. The results values are consistent in error range. G(S) of 0.10 and G(X) of 0.23 were obtained. As calculated, almost all the macromolecular radicals produced by chain scission were used for crosslinking. Also, the glass transition temperature of the RX-PES films increased with the increasing in the absorbed doses, while the glass transition temperature of the PES films irradiated at ambient temperature decreased with the increasing in the absorbed doses. The blending films of the PES with FEP or ETFE were prepared and the high temperature irradiation effects were also studies

Compartmentalization Technologies via Self-Assembly and Cross-Linking of Amphiphilic Random Block Copolymers in Water.

Science.gov (United States)

Matsumoto, Mayuko; Terashima, Takaya; Matsumoto, Kazuma; Takenaka, Mikihito; Sawamoto, Mitsuo

2017-05-31

Orthogonal self-assembly and intramolecular cross-linking of amphiphilic random block copolymers in water afforded an approach to tailor-make well-defined compartments and domains in single polymer chains and nanoaggregates. For a double compartment single-chain polymer, an amphiphilic random block copolymer bearing hydrophilic poly(ethylene glycol) (PEG) and hydrophobic dodecyl, benzyl, and olefin pendants was synthesized by living radical polymerization (LRP) and postfunctionalization; the dodecyl and benzyl units were incorporated into the different block segments, whereas PEG pendants were statistically attached along a chain. The copolymer self-folded via the orthogonal self-assembly of hydrophobic dodecyl and benzyl pendants in water, followed by intramolecular cross-linking, to form a single-chain polymer carrying double yet distinct hydrophobic nanocompartments. A single-chain cross-linked polymer with a chlorine terminal served as a globular macroinitiator for LRP to provide an amphiphilic tadpole macromolecule comprising a hydrophilic nanoparticle and a hydrophobic polymer tail; the tadpole thus self-assembled into multicompartment aggregates in water.

Post-modification by γ-radiation of VDF-based polymers: Electrochemical capacitor membrane application

International Nuclear Information System (INIS)

Dumas, L.

2012-01-01

This work deals with the modification of VDF-based polymer induced by γ-radiation as the polymer may be used in electrochemical super-capacitors. The main objective was to limit the swelling of the fluorinated matrix with a given electrolyte while a good wetting of the polymer by the liquid was also required. As the main basic process involved in polymer radiolysis is the formation of radicals, a part of the work was dedicated to the study of such species by using Electron Spin Resonance spectroscopy. A simulation model of ESR spectra was established in order to identify and quantify each radical species. The effect of several parameters such as radiation dose, annealing time or the nature of polymer matrix on the concentration of each species where investigated. A relation with the evolution of the crosslink density of the network formed during the radiolysis was proposed. In addition, one of the key steps of this work was to study the radiation crosslinking ability of VDF-based polymers and find a way to increase the crosslink density. This was achieved by incorporating, prior to the radiation process, a radiation sensitive cross linker: TAIC. Finally, a new strategy based on the modification of surface properties of PVDF was investigated. It consists in the radiation grafting of penta-fluor-styrene onto PVDF surface followed by the chemo-selective functionalization of the grafted segments. As a conclusion, the different approaches used in this thesis allowed us to understand the radiolysis of VDF-based polymers and take advantage of the elementary process involved in this type of chemistry, to build up robust and promising strategies for tuning properties. (author)

Analysis physical properties of composites polymer from cocofiber and polypropylene plastic waste with maleic anhydrate as crosslinking agent

Science.gov (United States)

Pelita, E.; Hidayani, T. R.; Akbar, A.

2017-07-01

This research was conducted with the aim to produce composites polymer with polypropylene plastic waste materials and cocofiber which aims to produce wood replacement material in the home furnishings industry. This research was conducted with several stages. The first stage is the process of soaking coco fiber with detergent to remove oil and 2% NaOH. The second stage is to combine the polypropylene plastic waste with cocofiber is a chemical bond, modification by adding maleic anhydride as a crosslinking agent and benzoyl peroxide as an initiator each as much as 1%. Mixing materials done by reflux method using xylene solvent. In this study, carried out a wide range of weight variation of coco fiber are added to the 10, 20, 30, 40 and 50%. The third stage is a polymer composite molding process using hot press at a temperature of 158°C. The results of polymer composites Showed optimum condition on the addition of 40% cocofiber with supple tensile strength value of 90.800 kgf /cm2 and value of elongation break at 3.6726 x 104 (kgf/cm2), melting point at 160.02°C, burning point 463.43°C, residue of TGA is 19%, the density of 0.84 g/mL. From these data, conclude that the resulting polymer composites meet the SNI 03-2105-2006 about ordinary composite polymer and polymer composite structural type 8 regular types from 17.5 to 10.5.

Effectiveness of trimethylopropane trimethacrylate for the electron-beam-irradiation-induced cross-linking of polylactic acid

Energy Technology Data Exchange (ETDEWEB)

Ng, Hon-Meng [Department of Chemical Engineering, Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Genting Kelang, 53300 Setapak, Kuala Lumpur (Malaysia); Bee, Soo-Tueen, E-mail: beest@utar.edu.my [Department of Chemical Engineering, Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Genting Kelang, 53300 Setapak, Kuala Lumpur (Malaysia); Ratnam, C.T. [Radiation Processing Technology Division, Malaysian Nuclear Agency, Bangi, 43000 Kajang, Selangor (Malaysia); Sin, Lee Tin; Phang, Yee-Yao; Tee, Tiam-Ting [Department of Chemical Engineering, Faculty of Engineering and Science, Universiti Tunku Abdul Rahman, Jalan Genting Kelang, 53300 Setapak, Kuala Lumpur (Malaysia); Rahmat, A.R. [Department of Polymer Engineering, Faculty of Chemical Engineering, Universiti Teknologi Malaysia, 81310 UTM Skudai, Johor (Malaysia)

2014-01-15

Highlights: • Investigation of trimethylopropane trimethacrylate (TMPTMA) on electron beam irradiated PLA. • Irradiated PLA blends were weakened by incorporation of high amount of TMPTMA. • TMPTMA interacts with polymer free radicals to build crosslinking network. -- Abstract: The purpose of this research was to investigate the effects of various loading levels of trimethylopropane trimethacrylate (TMPTMA) on the properties of polylactic acid (PLA) cross-linked via electron-beam irradiation. PLA was compounded with 3–5 wt.% of TMPTMA to induce cross-linking upon subjection to electron-beam irradiation doses of 25–250 kGy. The physical properties of the PLA samples were characterised by means of X-ray diffraction, gel fraction and scanning electron microscopy analyses on fractured surfaces after tensile tests. The presence of TMPTMA in PLA was found to effectively increase the crystallite size and gel fraction. However, higher loading levels of TMPTMA could compromise the properties of the PLA/TMPTMA samples, indicating that a larger amount of monomer free radicals might promote degradation within the substantially cross-linked amorphous phase. Irradiation-induced cross-linking in the samples could improve the cross-linking density while decreasing the elongation and interfering with the crystallisation. These effects are caused by the intensive irradiation-induced chain scission that is responsible for the deterioration of the mechanical and crystalline properties of the samples.

Effectiveness of trimethylopropane trimethacrylate for the electron-beam-irradiation-induced cross-linking of polylactic acid

International Nuclear Information System (INIS)

Ng, Hon-Meng; Bee, Soo-Tueen; Ratnam, C.T.; Sin, Lee Tin; Phang, Yee-Yao; Tee, Tiam-Ting; Rahmat, A.R.

2014-01-01

Highlights: • Investigation of trimethylopropane trimethacrylate (TMPTMA) on electron beam irradiated PLA. • Irradiated PLA blends were weakened by incorporation of high amount of TMPTMA. • TMPTMA interacts with polymer free radicals to build crosslinking network. -- Abstract: The purpose of this research was to investigate the effects of various loading levels of trimethylopropane trimethacrylate (TMPTMA) on the properties of polylactic acid (PLA) cross-linked via electron-beam irradiation. PLA was compounded with 3–5 wt.% of TMPTMA to induce cross-linking upon subjection to electron-beam irradiation doses of 25–250 kGy. The physical properties of the PLA samples were characterised by means of X-ray diffraction, gel fraction and scanning electron microscopy analyses on fractured surfaces after tensile tests. The presence of TMPTMA in PLA was found to effectively increase the crystallite size and gel fraction. However, higher loading levels of TMPTMA could compromise the properties of the PLA/TMPTMA samples, indicating that a larger amount of monomer free radicals might promote degradation within the substantially cross-linked amorphous phase. Irradiation-induced cross-linking in the samples could improve the cross-linking density while decreasing the elongation and interfering with the crystallisation. These effects are caused by the intensive irradiation-induced chain scission that is responsible for the deterioration of the mechanical and crystalline properties of the samples

Radiation Synthesis of Superabsorbent Polymers Based on Natural Polymers

International Nuclear Information System (INIS)

Sen, Murat; Hayrabolulu, Hande

2010-01-01

The objectives of proposed research contract were first synthesize superabsorbent polymers based on natural polymers to be used as disposable diapers and soil conditioning materials in agriculture, horticulture and other super adsorbent using industries. We have planned to use the natural polymers; locust beam gum, tara gum, guar gum and sodium alginate on the preparation of natural superabsorbent polymers(SAP). The aqueous solution of natural polymers and their blends with trace amount of monomer and cross-linking agents will be irradiated in paste like conditions by gamma rays for the preparation of cross-linked superabsorbent systems. The water absorption and deswellling capacity of prepared super adsorbents and retention capacity, absorbency under load, suction power, swelling pressure and pet-rewet properties will be determined. Use of these materials instead of synthetic super absorbents will be examined by comparing the performance of finished products. The experimental studies achieved in the second year of project mainly on the effect of radiation on the chemistry of sodium alginate polymers in different irradiation conditions and structure-property relationship particularly with respect to radiation induced changes on the molecular weight of natural polymers and preliminary studies on the synthesis of natural-synthetic hydride super adsorbent polymers were given in details

Insights into the swelling process and drug release mechanisms from cross-linked pectin/high amylose starch matrices

Directory of Open Access Journals (Sweden)

Fernanda M. Carbinatto

2014-02-01

Full Text Available Cross-linked pectin/high amylose mixtures were evaluated as a new excipient for matrix tablets formulations, since the mixing of polymers and cross-linking reaction represent rational tools to reach materials with modulated and specific properties that meet specific therapeutic needs. Objective: In this work the influence of polymer ratio and cross-linking process on the swelling and the mechanism driving the drug release from swellable matrix tablets prepared with this excipient was investigated. Methods: Cross-linked samples were characterized by their micromeritic properties (size and shape, density, angle of repose and flow rate and liquid uptake ability. Matrix tablets were evaluated according their physical properties and the drug release rates and mechanisms were also investigated. Results: Cross-linked samples demonstrated size homogeneity and irregular shape, with liquid uptake ability insensible to pH. Cross-linking process of samples allowed the control of drug release rates and the drug release mechanism was influenced by both polymer ratio and cross-linking process. The drug release of samples with minor proportion of pectin was driven by an anomalous transport and the increase of the pectin proportion contributed to the erosion of the matrix. Conclusion: The cross-linked mixtures of high amylose and pectin showed a suitable excipient for slowing the drug release rates.

Irradiatable polymer composition with improved oxidation resistance

International Nuclear Information System (INIS)

Lyons, B.J.

1977-01-01

A method is described for the incorporation of a substantially insoluble organic phosphite into a polymer composition such as polyolefin polymers or ethylene copolymers to prevent oxidation of the polymer at elevated temperatures after radiation-induced crosslinking. The crosslinking is readily achieved without affecting the antioxidant properties of the organic phosphite. Particularly suitable organic compounds are derivatives of pentaerythritol, dipentaerythritol, and tripentaerythritol in cooncentrations of 1 to 3% of the mixture to be irradiated

Control of polymer network topology in semi-batch systems

Science.gov (United States)

Wang, Rui; Olsen, Bradley; Johnson, Jeremiah

Polymer networks invariably possess topological defects: loops of different orders. Since small loops (primary loops and secondary loops) both lower the modulus of network and lead to stress concentration that causes material failure at low deformation, it is desirable to greatly reduce the loop fraction. We have shown that achieving loop fraction close to zero is extremely difficult in the batch process due to the slow decay of loop fraction with the polymer concentration and chain length. Here, we develop a modified kinetic graph theory that can model network formation reactions in semi-batch systems. We demonstrate that the loop fraction is not sensitive to the feeding policy if the reaction volume maintains constant during the network formation. However, if we initially put concentrated solution of small junction molecules in the reactor and continuously adding polymer solutions, the fractions of both primary loop and higher-order loops will be significantly reduced. There is a limiting value (nonzero) of loop fraction that can be achieved in the semi-batch system in condition of extremely slow feeding rate. This minimum loop fraction only depends on a single dimensionless variable, the product of concentration and with single chain pervaded volume, and defines an operating zone in which the loop fraction of polymer networks can be controlled through adjusting the feeding rate of the semi-batch process.

Radiation crosslinking of highly plasticized PVC

Science.gov (United States)

Mendizabal, E.; Cruz, L.; Jasso, C. F.; Burillo, G.; Dakin, V. I.

1996-02-01

To improve the physical properties of highly plasticized PVC, the polymer was crosslinked by gamma irradiation using a dose rate of 91 kGy/h. The effect of plasticizer type was studied by using three different plasticizers, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), di(2-ethyl hexyl) phthalate (DOP), and di(2-ethylhexyl terephthalate) (DOTP), and varying irradiation doses. Gel content was determined by soxhlet extraction, tensile measurements were made on a universal testing machine and the mechano-dynamic measurements were made in a dynamic rheometer. It was found that a considerable bonding of plasticizer molecules to macromolelcules takes place along with crosslinking, so that the use of the solvent extraction method for measuring the degree of crosslinking can give erroneous information. Radiation-chemical crosslinking yield ( Gc) and molecular weight of interjunctions chains ( Mc), were calculated for different systems studied. Addition of ethylene glycol dimethacrylate (EGDM) as a crosslinking coagent and dioctyl tin oxide (DOTO) as a stabilizer was also studied. Plasticizers extraction resistance was increased by irradiation treatment.

Radiation crosslinking of highly plasticized PVC

International Nuclear Information System (INIS)

Mendizabal, E.; Cruz, L.; Jasso, C.F.; Burillo, G.; Dakin, V.I.

1996-01-01

To improve the physical properties of highly plasticized PVC, the polymer was crosslinked by gamma irradiation using a dose rate of 91 kGy/h. The effect of plasticizer type was studied by using three different plasticizers, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), di(2-ethyl hexyl) phthalate (DOP), and di(2-ethylhexyl terephthalate) (DOTP), and varying irradiation doses. Gel content was determined by soxhlet extraction, tensile measurements were made on a universal testing machine and the mechano-dynamic measurements were made in a dynamic rheometer. It was found that a considerable bonding of plasticizer molecules to macromolecules takes place along with crosslinking, so that the use of the solvent extraction method for measuring the degree of crosslinking can give erroneous information. Radiation-chemical crosslinking yield (G c ) and molecular weight of interjunctions chains (M c ), were calculated for different systems studied. Addition of ethylene glycol dimethyacrylate (EGDM) as a crosslinking coagent and dioctyl tin oxide (DOTO) as a stabilizer was also studied. Plasticizers extraction resistance was increased by irradiation treatment. (author)

Crosslinked pullulan/cellulose acetate fibrous scaffolds for bone tissue engineering

Energy Technology Data Exchange (ETDEWEB)

Atila, Deniz [Department of Engineering Sciences, Middle East Technical University (Turkey); Keskin, Dilek [Department of Engineering Sciences, Middle East Technical University (Turkey); Biomaterials and Tissue Engineering Center of Excellence, Middle East Technical University (Turkey); Tezcaner, Ayşen, E-mail: tezcaner@metu.edu.tr [Department of Engineering Sciences, Middle East Technical University (Turkey); Biomaterials and Tissue Engineering Center of Excellence, Middle East Technical University (Turkey)

2016-12-01

Natural polymer based fibrous scaffolds have been explored for bone tissue engineering applications; however, their inadequate 3-dimensionality and poor mechanical properties are among the concerns for their use as bone substitutes. In this study, pullulan (P) and cellulose acetate (CA), two polysaccharides, were electrospun at various P/CA ratios (P{sub 80}/CA{sub 20}, P{sub 50}/CA{sub 50}, and P{sub 20}/CA{sub 80}%) to develop 3D fibrous network. The scaffolds were then crosslinked with trisodium trimetaphosphate (STMP) to improve the mechanical properties and to delay fast weight loss. The lowest weight loss was observed for the groups that were crosslinked with P/STMP 2/1 for 10 min. Fiber morphologies of P{sub 50}/CA{sub 50} were more uniform without phase separation and this group was crosslinked most efficiently among groups. It was found that mechanical properties of P{sub 20}/CA{sub 80} and P{sub 50}/CA{sub 50} were higher than that of P{sub 80}/CA{sub 20.} After crosslinking strain values of P{sub 50}/CA{sub 50} scaffolds were improved and these scaffolds became more stable. Unlike P{sub 80}/CA{sub 20,} uncrosslinked P{sub 50}/CA{sub 50} and P{sub 20}/CA{sub 80} were not lost in PBS. Among all groups, crosslinked P{sub 50}/CA{sub 50} scaffolds had more uniform pores; therefore this group was used for bioactivity and cell culture studies. Apatite-like structures were observed on fibers after SBF incubation. Human Osteogenic Sarcoma Cell Line (Saos-2) seeded onto crosslinked P{sub 50}/CA{sub 50} scaffolds adhered and proliferated. The functionality of cells was tested by measuring ALP activity of the cells and the results indicated their osteoblastic differentiation. In vitro tests showed that scaffolds were cytocompatible. To sum up, crosslinked P{sub 50}/CA{sub 50} scaffolds were proposed as candidate cell carriers for bone tissue engineering applications. - Highlights: • Crosslinked 3D electrospun P/CA scaffolds were prepared for the first time. • CA

Effect of crosslinker length on the elastic and compression modulus of poly(acrylamide) nanocomposite hydrogels

International Nuclear Information System (INIS)

Zaragoza, J; Chang, A; Asuri, P

2017-01-01

Polymer hydrogelshave shown to exhibit improved properties upon the addition of nanoparticles; however, the mechanical underpinnings behind these enhancements have not been fully elucidated. Moreover, fewer studies have focused on developing an understanding of how polymer parameters affect the nanoparticle-mediated enhancements. In this study, we investigated the elastic properties of silica nanoparticle-reinforced poly(acrylamide) hydrogels synthesized using crosslinkers of various lengths. Crosslinker length positively affected the mechanical properties of hydrogels that were synthesized with or without nanoparticles. However the degree of nanoparticle enhancement was negatively correlated to crosslinker length. Our findings enable the understanding of the respective roles of nanoparticle and polymer properties on nanoparticle-mediated enhancement of hydrogels and thereby the development of next-generation nanocomposite materials. (paper)

Computational modeling and molecular imprinting for the development of acrylic polymers with high affinity for bile salts.

Science.gov (United States)

Yañez, Fernando; Chianella, Iva; Piletsky, Sergey A; Concheiro, Angel; Alvarez-Lorenzo, Carmen

2010-02-05

This work has focused on the rational development of polymers capable of acting as traps of bile salts. Computational modeling was combined with molecular imprinting technology to obtain networks with high affinity for cholate salts in aqueous medium. The screening of a virtual library of 18 monomers, which are commonly used for imprinted networks, identified N-(3-aminopropyl)-methacrylate hydrochloride (APMA.HCl), N,N-diethylamino ethyl methacrylate (DEAEM) and ethyleneglycol methacrylate phosphate (EGMP) as suitable functional monomers with medium-to-high affinity for cholic acid. The polymers were prepared with a fix cholic acid:functional monomer mole ratio of 1:4, but with various cross-linking densities. Compared to polymers prepared without functional monomer, both imprinted and non-imprinted microparticles showed a high capability to remove sodium cholate from aqueous medium. High affinity APMA-based particles even resembled the performance of commercially available cholesterol-lowering granules. The imprinting effect was evident in most of the networks prepared, showing that computational modeling and molecular imprinting can act synergistically to improve the performance of certain polymers. Nevertheless, both the imprinted and non-imprinted networks prepared with the best monomer (APMA.HCl) identified by the modeling demonstrated such high affinity for the template that the imprinting effect was less important. The fitting of adsorption isotherms to the Freundlich model indicated that, in general, imprinting increases the population of high affinity binding sites, except when the affinity of the functional monomer for the target molecule is already very high. The cross-linking density was confirmed as a key parameter that determines the accessibility of the binding points to sodium cholate. Materials prepared with 9% mol APMA and 91% mol cross-linker showed enough affinity to achieve binding levels of up to 0.4 mmol g(-1) (i.e., 170 mg g(-1)) under flow

Nanoscale indent formation in shape memory polymers using a heated probe tip

Energy Technology Data Exchange (ETDEWEB)

Yang, F [Department of Mechanical Science and Engineering, University of Illinois Urbana-Champaign, Urbana, IL 61801 (United States); Wornyo, E [School of Electrical and Computer Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Gall, K [Department of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States); King, W P [Department of Mechanical Science and Engineering, University of Illinois Urbana-Champaign, Urbana, IL 61801 (United States)

2007-07-18

This paper presents experimental investigation of nanoscale indentation formation in shape memory polymers. The polymers were synthesized by photopolymerizing a tert-butyl acrylate (tBA) monomer with a poly(ethylene glycol dimethacrylate) (PEGDMA) crosslinker. The concentration and the molecular weight of the crosslinker were varied to produce five polymers with tailored properties. Nanoscale indentations were formed on the polymer surfaces by using a heated atomic force microscope (AFM) cantilever at various temperatures near or above the glass transition (between 84 and 215 deg. C) and a range of heating durations from 100 {mu}s to 8 ms. The images of the indents were obtained with the same probe tip at room temperature. The contact pressure, a measure of transient hardness, was derived from the indentation height data as a function of time and temperature for different polymers. With increasing crosslinker molecular weight and decreasing crosslinker concentration, the contact pressures decreased at a fixed maximum load due to increased crosslink spacing in the polymer system. The results provide insight into the nanoscale response of these novel materials.

Quantification of radiation induced crosslinking in a commercial, toughened silicone rubber, TR-55, by 1H MQ-NMR

Energy Technology Data Exchange (ETDEWEB)

Maxwell, R; Chinn, S; Alviso, C; Harvey, C A; Giuliani, J; Wilson, T; Cohenour, R

2008-11-10

Radiation induced degradation in a commercial, filled silicone composite has been studied by SPME/GC-MS, DMA, DSC, swelling, and Multiple Quantum NMR. Analysis of volatile and semivolatile species indicates degradation via decomposition of the peroxide curing catalyst and radiation induced backbiting reactions. DMA, swelling, and spin-echo NMR analysis indicate a increase in crosslink density of near 100% upon exposure to a cumulative dose of 250 kGray. Analysis of the sol-fraction via Charlseby-Pinner analysis indicates a ratio of chain scission to crosslinking yields of 0.38, consistent with the dominance of the crosslinking observed by DMA, swelling and spin-echo NMR and the chain scissioning reactions observed by MS analysis. Multiple Quantum NMR has revealed a bimodal distribution of residual dipolar couplings near 1 krad/sec and 5 krad/sec in an approximately 90:10 ratio, consistent with bulk network chains and chains associated with the filler surface. Upon exposure to radiation, the mean {Omega}{sub d} for both domains and the width of both domains both increased. The MQ NMR analysis provided increase insight into the effects of ionizing radiation on the network structure of silicone polymers.

Electrogenerated networks from poly[4-(diphenylaminobenzyl methacrylate] and their electrochromic properties

Directory of Open Access Journals (Sweden)

O. I. Negru

2014-09-01

Full Text Available Poly[4-(diphenylaminobenzyl methacrylate] with well-defined molecular weight and low polydispersity was prepared by atom transfer radical polymerization (ATRP using 4-(diphenylamino benzyl 2-bromo-2-methyl-propanoate as initiator and CuBr/2,2'-bipyridine as catalytic complex. Electrochemical behavior and optical properties of the polymers were investigated by cyclic voltammetry and UV-Vis and fluorescence spectroscopy. Cyclic votammetric studies revealed that the redox processes were accompanied by dimerization of triphenylamine pendant groups. The initial polymer was postmodified, in solution or bulk, by electrochemical oxidation leading to a crosslinked and insoluble network with electro -chromic properties, accompanied by strong color changes with high coloration efficiency. The crosslinking reaction took place between triphenylamine groups through para free positions leading to tetraphenylbenzidine bridges. The structure of polymers was confirmed by Fourier transform infrared (FT-IR spectroscopy and 1H and 13C-nuclear magnetic resonance spectroscopy. Morphology studies of the cross-linked film have evidenced a smooth and continuous aspect without any pinholes or defects.

Comparison of neat and photo-crosslinked polyvinylidene fluoride-co-hexafluoropropylene thin film dielectrics formed by spin-coating

Energy Technology Data Exchange (ETDEWEB)

Iyore, O.D.; Roodenko, K.; Winkler, P.S. [Materials Science and Engineering Department, The University of Texas at Dallas, Richardson, TX 75080 (United States); Noriega, J.R.; Vasselli, J.J. [Electrical Engineering Department, The University of Texas at Tyler, Tyler, TX 75799 (United States); Chabal, Y.J. [Materials Science and Engineering Department, The University of Texas at Dallas, Richardson, TX 75080 (United States); Gnade, B.E., E-mail: gnade@utdallas.edu [Materials Science and Engineering Department, The University of Texas at Dallas, Richardson, TX 75080 (United States)

2013-12-02

We report the characterization of photo-crosslinked polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP) thin film, metal–insulator–metal capacitors fabricated using standard semiconductor processing techniques. We characterize the capacitors using in-situ vibrational spectroscopy during thermally-assisted poling and correlate the Fourier transform infrared spectroscopy (FTIR) results with X-ray diffraction (XRD) results. FTIR analysis of the neat PVDF-HFP showed α → β transformations during poling at room temperature and at 55 °C. α → β transformations were observed for the crosslinked polymer only during poling at 55 °C. XRD data revealed that photo-crosslinking caused the polymer to partially crystallize into the β-phase. The similar behavior of the neat and crosslinked samples at 55 °C suggests that a higher activation energy was needed for α → β transformations in crosslinked PVDF-HFP during poling. Electrical measurements showed that photo-crosslinking had no significant effect on the dielectric constant and dielectric loss of PVDF-HFP. However, the dielectric strength and maximum energy density of the crosslinked polymer were severely reduced. - Highlights: • Polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) dielectrics were studied. • Phase transformations were observed only at 55 °C for the crosslinked PVDF-HFP. • Crosslinking had no strong effect on the dielectric constant of PVDF-HFP. • Breakdown strengths were 620 MVm{sup −1} and 362 MVm{sup −1} for neat and crosslinked films.

Development of new materials by utilizing radiation crosslinking

International Nuclear Information System (INIS)

Ueno, Keiji; Uda, Yujiro; Suzuki, Shizuo

1989-01-01

About 30 years have elapsed since the cables by electron beam crosslinking were developed as the first industrial utilization of radiation in Japan. At present about 200 electron beam accelerators are used industrially in Japan, and cable industry ranks at the top, followed by foaming polyethylene and curing, and the preliminary vulcanization of tires. The effect of these irradiations is the reforming of polymers by radiation crosslinking. In cables, the heat resistance and chemical resistance of insulators are improved by radiation crosslinking. By applying radiation crosslinking to polyurethane elastomer, its weakest point, waterproof property, was improved. Moreover, by using this crosslinked polyurethane elastomer for cable coating, the reliability of the sensor cables for brake system was able to be remarkably improved. As another new application of radiation crosslinking process, the improvement of the heat resistance of engineering plasties was examined. The structure of radiation crosslinked urethane elastomer cables, their endurance in hot water and oil, and the life, and the characteristics of sensor cables are reported. Multi-functional monomers, the molecular structure, and the various characteristics of engineering plastics are described. (K.I.)

Consequences of Morphology on Molecularly Imprinted Polymer-Ligand Recognition

Directory of Open Access Journals (Sweden)

Annika M. Rosengren

2013-01-01

Full Text Available The relationship between molecularly imprinted polymer (MIP morphology and template-rebinding over a series of warfarin-imprinted methacrylic acid co(ethylene dimethacrylate polymers has been explored. Detailed investigations of the nature of template recognition revealed that an optimal template binding was obtained with polymers possessing a narrow population of pores (~3–4 nm in the mesopore size range. Importantly, the warfarin-polymer rebinding analyses suggest strategies for regulating ligand binding capacity and specificity through variation of the degree of cross-linking, where polymers prepared with a lower degree of cross-linking afford higher capacity though non-specific in character. In contrast, the co-existence of specific and non-specific binding was found in conjunction with higher degrees of cross-linking and resultant meso- and macropore size distributions.

The characterisation of polymers using pulsed NMR

International Nuclear Information System (INIS)

Charlesby, A.

1983-01-01

Broad line pulsed NMR is applied to obtain information on radiation-induced polymer changes and other aspects of polymer science based on the interpretation of spin-spin relaxation curves. Calculations are made to determine the molecular weight, the crosslink density of simple, low molecular weight, flexible polymers. For higher molecular weight polymers, a conclusion can be drawn on the concentrations of entangled and crosslinked units by means of pulsed NMR. Some typical applications of the technique are illustrated by the examples of polyethylenes, rubbers, filled polymeric systems and aqueous polyethylene oxide solutions. The morphology of polymers can be followed by pulsed NMR. (V.N.)

Direct Photopatterning of Electrochromic Polymers

DEFF Research Database (Denmark)

Jensen, Jacob; Dyer, Aubrey L.; Shen, D. Eric

2013-01-01

Propylenedioxythiophene (ProDOT) polymers are synthesized using an oxidative polymerization route that results in methacrylate substituted poly(ProDOTs) having a Mn of 10–20 kDa wherein the methacrylate functionality constitutes from 6 to 60% of the total monomer units. Solutions of these polymers...... show excellent film forming abilities, with thin films prepared using both spray‐casting and spin‐coating. These polymers are demonstrated to crosslink upon UV irradiation at 350 nm, in the presence of an appropriate photoinitiator, to render the films insoluble to common organic solvents....... Electrochemical, spectroelectrochemical, and colorimetric analyses of the crosslinked polymer films are performed to establish that they retain the same electrochromic qualities as the parent polymers with no detriment to the observed properties. To demonstrate applicability for multi‐film processing...

Evaluation of Gentamicin and Lidocaine Release Profile from Gum Acacia-crosslinked-poly(2-hydroxyethylmethacrylate)-carbopol Based Hydrogels.

Science.gov (United States)

Singh, Baljit; Dhiman, Abhishek

2017-01-01

No doubt, the prevention of infection is an indispensable aspect of the wound management, but, simultaneous wound pain relief is also required. Therefore, herein this article, incorporation of antibiotic agent 'gentamicin' and pain relieving agent 'lidocaine' into hydrogel wound dressings, prepared by using acacia gum, carbopol and poly(2-hydroxyethylmethacrylate) polymers, has been carried out. The hydrogels were evaluated as a drug carrier for model drugs gentamicin and lidocaine. Synthesis of hydrogel wound dressing was carried out by free radical polymerization technique. The drug loading was carried out by swelling equilibrium method and gel strength of hydrogels was measured by a texture analyzer. Porous microstructure of the hydrogel was observed in cryo-SEM images. The hydrogel showed mesh size 37.29 nm, cross-link density 2.19× 10-5 mol/cm3, molecular weight between two cross-links 60.25× 10-3 g/mol and gel strength 0.625±0.112 N in simulated wound fluid. It is concluded that the pH of swelling medium has influenced the network structure of hydrogel i.e., molecular weight of the polymer chain between two neighboring cross links, crosslink density and the corresponding mesh size. A good correlation was established between gel strength and network parameters. Cryo-SEM images showed porous morphology of hydrogels. These hydrogels were found to be biodegradable and antimicrobial in nature. Drug release occurred through Fickian diffusion mechanism and release profile was best fitted in first order model. Overall it is concluded that modification in GA has led to formation of a porous hydrogels for wound dressing applications. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

EVA reactive blending with Si–H terminated polysiloxane by carbonyl hydrosilylation reaction: From compatibilised blends to crosslinking networks

International Nuclear Information System (INIS)

Bonnet, J.; Bounor-Legaré, V.; Alcouffe, P.; Cassagnau, P.

2012-01-01

A new and original method based on carbonyl hydrosilylation was developed to prepare ethylene-vinyl acetate (EVA)/polysiloxane polymer blends. This focused on the addition of hydrogenosilane groups (SiH) from polysiloxane to the carbonyl groups of EVA. The influence of the nature of the polysiloxane on blend properties was investigated by rheology and scanning electron microscopy. Mixing of a low viscosity polysiloxane with a high viscosity EVA matrix produced a two-phase morphology. The occurrence of the hydrosilylation reaction at the EVA/polysiloxane interface promoted a homogenisation of the blend depending on the molar ratio SiH/vinyl acetate groups, [SiH]/[VA], and the viscosity ratio of the blend. Two distinct behaviours were observed. The formation of a crosslinked network under shear was obtained for a low viscosity ratio between polysiloxane and EVA (λ polysiloxane/EVA = 4.0 × 10 −6 ) with a high concentration of SiH groups ([SiH]/[VA] = 0.5), while the formation of a compatibilised blend was observed for high molar mass polysiloxanes (Mn > 15,000 g mol −1 ) with a low concentration of SiH ([SiH]/[VA] −3 ). -- Highlights: ► Carbonyl hydrosilylation reaction was found to enhance EVA/polysiloxane immiscible blends. ► EVA crosslinking was obtained with a low molar mass polysiloxane. ► EVA compatibilisation was obtained with a high molar mass polysiloxane. ► Shear rate was found to improve the hydrosilylation reaction at the interface. ► A two-phase morphology of the blends was observed after reaction with fine polysiloxane nodules.

Carboxymethylcellulose hydrogel crosslinked with citric acid for biomedical application

International Nuclear Information System (INIS)

Capanema, Nadia S.V.; Mansur, Alexandra A.P.; Mansur, Herman S.; Universidade Federal de Minas Gerais

2016-01-01

The carboxymethylcellulose (CMCel) has been extensively used in order application as flexible polymer membrane. Biopolymers crosslinked have been studied to optimize their performance in biomedical applications. In this work, CMCel films with a degree of substitution (DS = 0.77) were prepared by evaporation of solvent and crosslinked with different concentrations of citric acid (CA). The synthesized CMCel was characterized by Infrared Spectroscopy by Fourier Transform X-ray spectroscopy (FTIR), and morphology assessed by scanning electron microscopy (SEM). Morphological analysis performed using the SEM indicated the crosslinked CMCel and not crosslinked with a very smooth and uniform appearance. The FTIR results indicated the modification of existing bands and appearance of a new band 1715 cm"-"1 suggesting that there has been change in the structure of the crosslinked CMCel. (author)

Mechanical properties of polymer-infiltrated-ceramic-network materials.

Science.gov (United States)

Coldea, Andrea; Swain, Michael V; Thiel, Norbert

2013-04-01

To determine and identify correlations between flexural strength, strain at failure, elastic modulus and hardness versus ceramic network densities of a range of novel polymer-infiltrated-ceramic-network (PICN) materials. Four ceramic network densities ranging from 59% to 72% of theoretical density, resin infiltrated PICN as well as pure polymer and dense ceramic cross-sections were subjected to Vickers Indentations (HV 5) for hardness evaluation. The flexural strength and elastic modulus were measured using three-point-bending. The fracture response of PICNs was determined for cracks induced by Vickers-indentation. Optical and scanning electron microscopy (SEM) was employed to observe the indented areas. Depending on the density of the porous ceramic the flexural strength of PICNs ranged from 131 to 160MPa, the hardness values ranged between 1.05 and 2.10GPa and the elastic modulus between 16.4 and 28.1GPa. SEM observations of the indentation induced cracks indicate that the polymer network causes greater crack deflection than the dense ceramic material. The results were compared with simple analytical expressions for property variation of two phase composite materials. This study points out the correlation between ceramic network density, elastic modulus and hardness of PICNs. These materials are considered to more closely imitate natural tooth properties compared with existing dental restorative materials. Copyright © 2013 Academy of Dental Materials. All rights reserved.

The properties of water in swollen cross-linked polystyrene sulfo acids

Science.gov (United States)

Gagarin, A. N.; Tokmachev, M. G.; Kovaleva, S. S.; Ferapontov, N. B.

2008-11-01

The properties of water in polystyrene sulfo acid gels with various cross-linking degrees were studied by optical volumetry and dynamic desorption porosimetry. The isotherms of water desorption obtained by dynamic desorption porosimetry coincided with isopiestic isotherms, which allowed this method to be recommended for the determination of the amount of water in polymer gels. Joint optical volumetry and dynamic desorption porosimetry studies showed that the interphase boundary in the cross-liked hydrophilic polymer-water system did not coincide with the visible gel boundary, because gels were two-phase systems, which contained water of two types, “free” and “bound.” The influence of the degree of polymer cross-linking on the amounts and properties of water of the two types was studied. It was shown that constants of water distribution in the polymer could be calculated from the dynamic desorption porosimetry data.

Crosslinking of electrospun poly (VDF-co-HFP) nanofibrous membranes by gamma-ray irradiation

International Nuclear Information System (INIS)

Kim, Yun Hye; Lim, Youn Mook; Choi, Jae Hak; An, Sung Jun; Park, Jong Seok; Nho, Young Chang

2008-01-01

Poly (VDF-co-HFP)/PEGDMA nanofibrous membranes (NFMs) have been prepared by an electrospinning process. Since electrospun NFMs have a nanoporous structure, they have a potential application for a polymer electrolyte or a separator. Poly (VDF-co-HFP) is a polymer electrolyte binder. In order to improve their mechanical properties, poly (VDF-co-HFP)/PEGDMA NFMs were crosslinked by a gamma-ray irradiation. Then the crosslinked NFMs were characterized through an electrolyte uptake, IR structural analysis, and SEM morphological investigation

Preparation and physico-chemical properties of hydrogels from carboxymethyl cassava starch crosslinked with citric acid

Science.gov (United States)

Boonkham, Sasikan; Sangseethong, Kunruedee; Chatakanon, Pathama; Niamnuy, Chalida; Nakasaki, Kiyohiko; Sriroth, Klanarong

2014-06-01

Recently, environmentally friendly hydrogels prepared from renewable bio-based resources have drawn significant attention from both industrial and academic sectors. In this study, chemically crosslinked hydrogels have been developed from cassava starch which is a bio-based polymer using a non-toxic citric acid as a crosslinking agent. Cassava starch was first modified by carboxymethylation to improve its water absorbency property. The carboxymethyl cassava starch (CMCS) obtained was then crosslinked with citric acid at different concentrations and reaction times. The gel fraction of hydrogels increased progressively with increasing citric acid concentration. Free swelling capacity of hydrogels in de-ionized water, saline solution and buffers at various pHs as well as absorption under load were investigated. The results revealed that swelling behavior and mechanical characteristic of hydrogels depended on the citric acid concentration used in reaction. Increasing citric acid concentration resulted in hydrogels with stronger network but lower swelling and absorption capacity. The cassava starch hydrogels developed were sensitive to ionic strength and pH of surrounding medium, showing much reduced swelling capacity in saline salt solution and acidic buffers.

Density crosslink study of gamma irradiated LDPE predicted by gel-fraction, swelling and glass transition temperature characterization

International Nuclear Information System (INIS)

Cardoso, Elisabeth C.L.; Scagliusi, Sandra R.; Moraes, Guilherme F.; Ono, Lilian S.; Parra, D.F.; Lugao, Ademar B.

2011-01-01

Experimental results showed that the crosslink density of polymeric stocks may be predicted from values of gel content based on the reactive portion of the stocks, that is, exclusive of plasticizers and fillers. Where entanglements may be neglected, the crosslink density is directly proportional to functions of the gel and sol contents. In order to predict the behavior of carbon-chain polymers exposed to ionizing radiation, an empirical rule can be used. According to this rule, polymers containing a hydrogen atom at each carbon atom predominantly undergo crosslinking. During irradiation, chain scission occurs simultaneously and competitively with crosslinking, the end result being determined by the ratio of the yields of the two reactions. The ratio of crosslinking to scission depends basically on factors including total irradiation dose, dose rate and the presence of oxygen. The glass transition temperature (Tg), temperature below which the polymer segments do not have sufficient energy to move past one another, marks the onset of segmental mobility for a polymer. Properties such as melt index, melt strength, crystallinity, glass transition, gel fraction, swelling ratio and elasticity modulus were assessed in LDPE (2.6 g.10 min -1 melt index) gamma irradiated within a 10, 15, 20 and 30 kGy and results obtained were further discussed prior conclusion. (author)

Enzymatic cross-linking of human recombinant elastin (HELP) as biomimetic approach in vascular tissue engineering.

Science.gov (United States)

Bozzini, Sabrina; Giuliano, Liliana; Altomare, Lina; Petrini, Paola; Bandiera, Antonella; Conconi, Maria Teresa; Farè, Silvia; Tanzi, Maria Cristina

2011-12-01

The use of polymers naturally occurring in the extracellular matrix (ECM) is a promising strategy in regenerative medicine. If compared to natural ECM proteins, proteins obtained by recombinant DNA technology have intrinsic advantages including reproducible macromolecular composition, sequence and molecular mass, and overcoming the potential pathogens transmission related to polymers of animal origin. Among ECM-mimicking materials, the family of recombinant elastin-like polymers is proposed for drug delivery applications and for the repair of damaged elastic tissues. This work aims to evaluate the potentiality of a recombinant human elastin-like polypeptide (HELP) as a base material of cross-linked matrices for regenerative medicine. The cross-linking of HELP was accomplished by the insertion of cross-linking sites, glutamine and lysine, in the recombinant polymer and generating ε-(γ-glutamyl) lysine links through the enzyme transglutaminase. The cross-linking efficacy was estimated by infrared spectroscopy. Freeze-dried cross-linked matrices showed swelling ratios in deionized water (≈2500%) with good structural stability up to 24 h. Mechanical compression tests, performed at 37°C in wet conditions, in a frequency sweep mode, indicated a storage modulus of 2/3 kPa, with no significant changes when increasing number of cycles or frequency. These results demonstrate the possibility to obtain mechanically resistant hydrogels via enzymatic crosslinking of HELP. Cytotoxicity tests of cross-linked HELP were performed with human umbilical vein endothelial cells, by use of transwell filter chambers for 1-7 days, or with its extracts in the opportune culture medium for 24 h. In both cases no cytotoxic effects were observed in comparison with the control cultures. On the whole, the results suggest the potentiality of this genetically engineered HELP for regenerative medicine applications, particularly for vascular tissue regeneration.

The Alginate Demonstration: Polymers, Food Science, and Ion Exchange

Science.gov (United States)

Waldman, Amy Sue; Schechinger, Linda; Govindarajoo, Geeta; Nowick, James S.; Pignolet, Louis H.

1998-11-01

We have recently devised a polymer demonstration involving the crosslinking and decrosslinking of alginate, a polysaccharide isolated from seaweed. The polymer is composed of D-mannuronic acid and L-guluronic acid subunits and is a component of cell walls. It is commonly used as a thickener in foods such as ice cream and fruit-filled snacks. For the demonstration, a 2% solution of sodium alginate is poured into a 1% solution of calcium chloride. Nontoxic calcium alginate "worms" form due to crosslinking of the polymer. Alternatively, the commercially available antacid Gaviscon can be used as a source of sodium alginate. The crosslinks can then be broken by shaking the worms in brine. The demonstration is a fine addition to any chemical educator's repertoire of polymer experiments.

Radiation crosslinking of elastomers

International Nuclear Information System (INIS)

Pearson, D.S.

1981-01-01

In the first part of this paper a review is presented of recent results which show that the tensile strength and fatigue life of synthetic elastomers cured by radiation are essentially equivalent to those prepared by other crosslinking techniques. An explanation for the conflict of these new results with the earlier studies on natural rubber is presented. Investigations into the mechanisms and kinetics of crosslinking mentioned above have also shown that the irradiation method should be ideal for preparing well characterized networks. Such materials are useful for testing theoretical relationships between the structure of rubber networks and their stress-strain behavior. The second part of this paper is devoted to this aspect. (author)

Crosslinked polytriazole membranes for organophilic filtration

KAUST Repository

Chisca, Stefan

2016-12-30

We report the preparation of crosslinked membranes for organophilic filtration, by reacting a new polytriazole with free OH groups, using non-toxic poly (ethylene glycol) diglycidyl ether (PEGDE). The OH-functionalized polymer was obtained by converting the oxadiazole to triazole rings with high yield (98%). The maximum degree of crosslinking is achieved after 6 h of reaction. The crosslinked polytriazole membranes are stable in a wide range of organic solvents and show high creep recovery, indicating the robustness of crosslinked membranes. The influence of different casting solutions and different crosslinking time on the membrane morphology and membrane performance was investigated. The membranes performance was studied in dimethylformamide (DMF) and (tetrahydrofuran) THF. We achieved a permeance for THF of 49 L m−2 h−1 bar−1 for membranes with molecular weight cut off (MWCO) of 7 kg mol−1 and a permeance for THF of 17.5 L m−2 h−1 bar−1 for membranes with MWCO of 3 kg mol−1. Our data indicate that by using the new polytriazole is possible to adjust the pore dimensions of the membranes to have a MWCO, which covers ultra- and nanofiltration range.

Crosslinked polytriazole membranes for organophilic filtration

KAUST Repository

Chisca, Stefan; Falca, Gheorghe; Musteata, Valentina-Elena; Boi, Cristiana; Nunes, Suzana Pereira

2016-01-01

We report the preparation of crosslinked membranes for organophilic filtration, by reacting a new polytriazole with free OH groups, using non-toxic poly (ethylene glycol) diglycidyl ether (PEGDE). The OH-functionalized polymer was obtained by converting the oxadiazole to triazole rings with high yield (98%). The maximum degree of crosslinking is achieved after 6 h of reaction. The crosslinked polytriazole membranes are stable in a wide range of organic solvents and show high creep recovery, indicating the robustness of crosslinked membranes. The influence of different casting solutions and different crosslinking time on the membrane morphology and membrane performance was investigated. The membranes performance was studied in dimethylformamide (DMF) and (tetrahydrofuran) THF. We achieved a permeance for THF of 49 L m−2 h−1 bar−1 for membranes with molecular weight cut off (MWCO) of 7 kg mol−1 and a permeance for THF of 17.5 L m−2 h−1 bar−1 for membranes with MWCO of 3 kg mol−1. Our data indicate that by using the new polytriazole is possible to adjust the pore dimensions of the membranes to have a MWCO, which covers ultra- and nanofiltration range.

Effect of chain rigidity on network architecture and deformation behavior of glassy polymer networks

Science.gov (United States)

Knowles, Kyler Reser

Processing carbon fiber composite laminates creates molecular-level strains in the thermoset matrix upon curing and cooling which can lead to failures such as geometry deformations, micro-cracking, and other issues. It is known strain creation is attributed to the significant volume and physical state changes undergone by the polymer matrix throughout the curing process, though storage and relaxation of cure-induced strains remain poorly understood. This dissertation establishes two approaches to address the issue. The first establishes testing methods to simultaneously measure key volumetric properties of a carbon fiber composite laminate and its polymer matrix. The second approach considers the rigidity of the polymer matrix in regards to strain storage and relaxation mechanisms which ultimately control composite performance throughout manufacturing and use. Through the use of a non-contact, full-field strain measurement technique known as digital image correlation (DIC), we describe and implement useful experiments which quantify matrix and composite parameters necessary for simulation efforts and failure models. The methods are compared to more traditional techniques and show excellent correlation. Further, we established relationships which represent matrix-fiber compatibility in regards to critical processing constraints. The second approach involves a systematic study of epoxy-amine networks which are chemically-similar but differ in chain segment rigidity. Prior research has investigated the isomer effect of glassy polymers, showing sizeable differences in thermal, volumetric, physical, and mechanical properties. This work builds on these themes and shows the apparent isomer effect is rather an effect of chain rigidity. Indeed, it was found that structurally-dissimilar polymer networks exhibit very similar properties as a consequence of their shared average network rigidity. Differences in chain packing, as a consequence of chain rigidity, were shown to

Antibiofouling hybrid dendritic Boltorn/star PEG thiol-ene cross-linked networks.

Science.gov (United States)

Bartels, Jeremy W; Imbesi, Philip M; Finlay, John A; Fidge, Christopher; Ma, Jun; Seppala, Jonathan E; Nystrom, Andreas M; Mackay, Michael E; Callow, James A; Callow, Maureen E; Wooley, Karen L

2011-06-01

A series of thiol-ene generated amphiphilic cross-linked networks was prepared by reaction of alkene-modified Boltorn polyesters (Boltorn-ene) with varying weight percent of 4-armed poly(ethylene glycol) (PEG) tetrathiol (0-25 wt%) and varying equivalents of pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) (0-64 wt%). These materials were designed to present complex surface topographies and morphologies, with heterogeneity of surface composition and properties and robust mechanical properties, to serve as nontoxic antibiofouling coatings that are amenable to large-scale production for application in the marine environment. Therefore, a two-dimensional matrix of materials compositions was prepared to study the physical and mechanical properties, over which the compositions spanned from 0 to 25 wt% PEG tetrathiol and 0-64 wt% PETMP (the overall thiol/alkene (SH/ene) ratios ranged from 0.00 to 1.00 equiv), with both cross-linker weight percentages calculated with respect to the weight of Boltorn-ene. The Boltorn-ene components were prepared through the esterification of commercially available Boltorn H30 with 3-butenoic acid. The subsequent cross-linking of the Boltorn-PEG-PETMP films was monitored using IR spectroscopy, where it was found that near-complete consumption of both thiol and alkene groups occurred when the stoichiometry was ca. 48 wt% PETMP (0.75 equiv SH/ene, independent of PEG amount). The thermal properties of the films showed an increase in T(g) with an increase in 4-armed PEG-tetrathiol wt%, regardless of the PETMP concentration. Investigation of the bulk mechanical properties in dry and wet states found that the Young's modulus was the greatest at 48 wt% PETMP (0.75 equiv of SH/ene). The ultimate tensile strength increased when PETMP was constant and the PEG concentration was increased. The Young's modulus was slightly lower for wet films at constant PEG or constant PETMP amounts, than for the dry samples. The nanoscopic surface features were

Controlled Aloin Release from Crosslinked Polyacrylamide Hydrogels: Effects of Mesh Size, Electric Field Strength and a Conductive Polymer

Directory of Open Access Journals (Sweden)

Anuvat Sirivat

2013-10-01

Full Text Available The aim of this paper is to investigate the effects of hydrogel mesh size, a conductive polymer, and electric field strength on controlled drug delivery phenomena using drug-loaded polyacrylamide hydrogels prepared at various crosslinking ratios both with and without a conductive polymer system. Poly(p-phenylene vinylene, PPV, as the model conductive polymer, was used to study its ability to control aloin released from aloin-doped poly(p-phenylene vinylene/polyacrylamide hydrogel (aloin-doped PPV/PAAM. In the passive release, the diffusion of aloin from five aloin-doped PPV/PAAM hydrogel systems each was delayed ranging from during the first three hours to during the first 14 h due to the ionic interaction between the anionic drug and PPV. After the delayed periods, aloin could diffuse continuously into the buffer solution through the PAAM matrix. The amount of aloin released from the aloin-doped PPV/PAAM rose with increasing electric field strength as a result of the three mechanisms: the expansion of PPV chains inside the hydrogel, iontophoresis, and the electroporation of the matrix pore size, combined. Furthermore, the conductive polymer and the electric field could be used in combination to regulate the amount of release drug to a desired level, to control the release rate, and to switch the drug delivery on/off.

Equilibrium & Nonequilibrium Fluctuation Effects in Biopolymer Networks

Science.gov (United States)

Kachan, Devin Michael

Fluctuation-induced interactions are an important organizing principle in a variety of soft matter systems. In this dissertation, I explore the role of both thermal and active fluctuations within cross-linked polymer networks. The systems I study are in large part inspired by the amazing physics found within the cytoskeleton of eukaryotic cells. I first predict and verify the existence of a thermal Casimir force between cross-linkers bound to a semi-flexible polymer. The calculation is complicated by the appearance of second order derivatives in the bending Hamiltonian for such polymers, which requires a careful evaluation of the the path integral formulation of the partition function in order to arrive at the physically correct continuum limit and properly address ultraviolet divergences. I find that cross linkers interact along a filament with an attractive logarithmic potential proportional to thermal energy. The proportionality constant depends on whether and how the cross linkers constrain the relative angle between the two filaments to which they are bound. The interaction has important implications for the synthesis of biopolymer bundles within cells. I model the cross-linkers as existing in two phases: bound to the bundle and free in solution. When the cross-linkers are bound, they behave as a one-dimensional gas of particles interacting with the Casimir force, while the free phase is a simple ideal gas. Demanding equilibrium between the two phases, I find a discontinuous transition between a sparsely and a densely bound bundle. This discontinuous condensation transition induced by the long-ranged nature of the Casimir interaction allows for a similarly abrupt structural transition in semiflexible filament networks between a low cross linker density isotropic phase and a higher cross link density bundle network. This work is supported by the results of finite element Brownian dynamics simulations of semiflexible filaments and transient cross-linkers. I

Catalytic molecularly imprinted polymer membranes: development of the biomimetic sensor for phenols detection.

Science.gov (United States)

Sergeyeva, T A; Slinchenko, O A; Gorbach, L A; Matyushov, V F; Brovko, O O; Piletsky, S A; Sergeeva, L M; Elska, G V

2010-02-05

Portable biomimetic sensor devices for the express control of phenols content in water were developed. The synthetic binding sites mimicking active site of the enzyme tyrosinase were formed in the structure of free-standing molecularly imprinted polymer membranes. Molecularly imprinted polymer membranes with the catalytic activity were obtained by co-polymerization of the complex Cu(II)-catechol-urocanic acid ethyl ester with (tri)ethyleneglycoldimethacrylate, and oligourethaneacrylate. Addition of the elastic component oligourethaneacrylate provided formation of the highly cross-linked polymer with the catalytic activity in a form of thin, flexible, and mechanically stable membrane. High accessibility of the artificial catalytic sites for the interaction with the analyzed phenol molecules was achieved due to addition of linear polymer (polyethyleneglycol Mw 20,000) to the initial monomer mixture before the polymerization. As a result, typical semi-interpenetrating polymer networks (semi-IPNs) were formed. The cross-linked component of the semi-IPN was represented by the highly cross-linked catalytic molecularly imprinted polymer, while the linear one was represented by polyethyleneglycol Mw 20,000. Extraction of the linear polymer from the fully formed semi-IPN resulted in formation of large pores in the membranes' structure. Concentration of phenols in the analyzed samples was detected using universal portable device oxymeter with the oxygen electrode in a close contact with the catalytic molecularly imprinted polymer membrane as a transducer. The detection limit of phenols detection using the developed sensor system based on polymers-biomimics with the optimized composition comprised 0.063 mM, while the linear range of the sensor comprised 0.063-1 mM. The working characteristics of the portable sensor devices were investigated. Storage stability of sensor systems at room temperature comprised 12 months (87%). As compared to traditional methods of phenols

Modeling the controllable pH-responsive swelling and pore size of networked alginate based biomaterials.

Science.gov (United States)

Chan, Ariel W; Neufeld, Ronald J

2009-10-01

Semisynthetic network alginate polymer (SNAP), synthesized by acetalization of linear alginate with di-aldehyde, is a pH-responsive tetrafunctionally linked 3D gel network, and has potential application in oral delivery of protein therapeutics and active biologicals, and as tissue bioscaffold for regenerative medicine. A constitutive polyelectrolyte gel model based on non-Gaussian polymer elasticity, Flory-Huggins liquid lattice theory, and non-ideal Donnan membrane equilibria was derived, to describe SNAP gel swelling in dilute and ionic solutions containing uni-univalent, uni-bivalent, bi-univalent or bi-bi-valent electrolyte solutions. Flory-Huggins interaction parameters as a function of ionic strength and characteristic ratio of alginates of various molecular weights were determined experimentally to numerically predict SNAP hydrogel swelling. SNAP hydrogel swells pronouncedly to 1000 times in dilute solution, compared to its compact polymer volume, while behaving as a neutral polymer with limited swelling in high ionic strength or low pH solutions. The derived model accurately describes the pH-responsive swelling of SNAP hydrogel in acid and alkaline solutions of wide range of ionic strength. The pore sizes of the synthesized SNAP hydrogels of various crosslink densities were estimated from the derived model to be in the range of 30-450 nm which were comparable to that measured by thermoporometry, and diffusion of bovine serum albumin. The derived equilibrium swelling model can characterize hydrogel structure such as molecular weight between crosslinks and crosslinking density, or can be used as predictive model for swelling, pore size and mechanical properties if gel structural information is known, and can potentially be applied to other point-link network polyelectrolytes such as hyaluronic acid gel.

Absorbed energy for radiation crosslinking in stabilized PE systems

International Nuclear Information System (INIS)

Novakovic, Lj.; Gal, O.; Charlesby, A.

1990-01-01

A quantitative consideration on the absorbed energy consumption in various γ-irradiated polyethylene systems is given. On the base of the increased gel dose values for the PE systems containing antioxidant, relative to the gel doses for the pure polymers, the surplus of the absorbed energy due to the presence of the particular antioxidant is calculated. The increasing of the energy consumption in the stabilized systems depends on both the type and the content of the basic polymer. The surplus in the absorbed energy decreases with the radiation dose increasing, reflecting both the diminishing of the antioxidant concentration in the irradiating PE systems and the crosslinking level. The findings can be of interest in the estimation of the absorbed doses for the specific radiation crosslinking processes. (author)

Absorbed energy for radiation crosslinking in stabilized PE systems

Energy Technology Data Exchange (ETDEWEB)

Novakovic, Lj; Gal, O [Institut za Nuklearne Nauke Boris Kidric, Belgrade (Yugoslavia); Charlesby, A

1990-01-01

A quantitative consideration on the absorbed energy consumption in various {gamma}-irradiated polyethylene systems is given. On the base of the increased gel dose values for the PE systems containing antioxidant, relative to the gel doses for the pure polymers, the surplus of the absorbed energy due to the presence of the particular antioxidant is calculated. The increasing of the energy consumption in the stabilized systems depends on both the type and the content of the basic polymer. The surplus in the absorbed energy decreases with the radiation dose increasing, reflecting both the diminishing of the antioxidant concentration in the irradiating PE systems and the crosslinking level. The findings can be of interest in the estimation of the absorbed doses for the specific radiation crosslinking processes. (author).

Nanoporous thermosetting polymers.

Science.gov (United States)

Raman, Vijay I; Palmese, Giuseppe R

2005-02-15

Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface.

Moisture curable toughened poly(lactide utilizing vinyltrimethoxysilane based crosslinks

Directory of Open Access Journals (Sweden)

J. Schneider

2016-10-01

Full Text Available Vinyltrimethoxysilane (VTMOS was grafted on to the backbone of poly(lactide (PLA through a free radical grafting reaction using reactive extrusion (REX processing. The methoxy groups of the silane provide the modified PLA sites for crosslinking through a moisture induced pathway. VTMOS grafting efficiencies of up to 90% were obtained. The newly created methoxy functionality of the modified PLA readily undergoes hydrolysis and condensation forming siloxane crosslinks in the material. Crosslinking with VTMOS exhibited improved modulus, strength, and impact toughness while showing a decrease in ductility. Incorporating silanol-terminated poly(dimethylsiloxane (OH-PDMS resulted in the formation of longer siloxane crosslinks. These samples showed an increase in modulus and impact toughness due to the crosslinking, while the longer siloxane linkages resulted in improved ductility and tensile toughness. This is unusual for polymers toughened through crosslinking reactions. Scanning Electron Microscopy (SEM of the fractured surfaces showed the presence of these elongated siloxane crosslinks. This enhanced ability for the modified PLA to deform and absorb energy results in the increase in both impact and tensile toughness.

Stable and biocompatible genipin-inducing interlayer-crosslinked micelles for sustained drug release

Energy Technology Data Exchange (ETDEWEB)

Dai, Yu; Zhang, Xiaojin, E-mail: zhangxj@cug.edu.cn [China University of Geosciences, Faculty of Materials Science and Chemistry (China)

2017-05-15

To develop the sustained drug release system, here we describe genipin-inducing interlayer-crosslinked micelles crosslinked via Schiff bases between the amines of amphiphilic linear-hyperbranched polymer poly(ethylene glycol)-branched polyethylenimine-poly(ε-caprolactone) (PEG-PEI-PCL) and genipin. The generation of Schiff bases was confirmed by the color changes and UV-Vis absorption spectra of polymeric micelles after adding genipin. The particle size, morphology, stability, in vitro cytotoxicity, drug loading capacity, and in vitro drug release behavior of crosslinked micelles as well as non-crosslinked micelles were characterized. The results indicated that genipin-inducing interlayer-crosslinked micelles had better stability and biocompatibility than non-crosslinked micelles and glutaraldehyde-inducing interlayer-crosslinked micelles. In addition, genipin-inducing interlayer-crosslinked micelles were able to improve drug loading capacity, reduce the initial burst release, and achieve sustained drug release.

Covalently Cross-Linked Sulfone Polybenzimidazole Membranes with Poly(Vinylbenzyl Chloride) for Fuel Cell Applications

DEFF Research Database (Denmark)

Yang, Jingshuai; Aili, David; Li, Qingfeng

2013-01-01

Covalently cross-linked polymer membranes were fabricated from poly(aryl sulfone benzimidazole) (SO(2) PBI) and poly(vinylbenzyl chloride) (PVBCl) as electrolytes for high-temperature proton-exchange-membrane fuel cells. The cross-linking imparted organo insolubility and chemical stability against...

Tailoring the mechanical properties by molecular integration of flexible and stiff polymer networks.

Science.gov (United States)

Wan, Haixiao; Shen, Jianxiang; Gao, Naishen; Liu, Jun; Gao, Yangyang; Zhang, Liqun

2018-03-28

Designing a multiple-network structure at the molecular level to tailor the mechanical properties of polymeric materials is of great scientific and technological importance. Through the coarse-grained molecular dynamics simulation, we successfully construct an interpenetrating polymer network (IPN) composed of a flexible polymer network and a stiff polymer network. First, we find that there is an optimal chain stiffness for a single network (SN) to achieve the best stress-strain behavior. Then we turn to study the mechanical behaviors of IPNs. The result shows that the stress-strain behaviors of the IPNs appreciably exceed the sum of that of the corresponding single flexible and stiff network, which highlights the advantage of the IPN structure. By systematically varying the stiffness of the stiff polymer network of the IPNs, optimal stiffness also exists to achieve the best performance. We attribute this to a much larger contribution of the non-bonded interaction energy. Last, the effect of the component concentration ratio is probed. With the increase of the concentration of the flexible network, the stress-strain behavior of the IPNs is gradually enhanced, while an optimized concentration (around 60% molar ration) of the stiff network occurs, which could result from the dominant role of the enthalpy rather than the entropy. In general, our work is expected to provide some guidelines to better tailor the mechanical properties of the IPNs made of a flexible network and a stiff network, by manipulating the stiffness of the stiff polymer network and the component concentration ratio.

Selective Photophysical Modification on Light-Emitting Polymer Films for Micro- and Nano-Patterning

Directory of Open Access Journals (Sweden)

Xinping Zhang

2016-02-01

Full Text Available Laser-induced cross-linking in polymeric semiconductors was utilized to achieve micro- and nano-structuring in thin films. Single- and two-photon cross-linking processes led to the reduction in both the refractive index and thickness of the polymer films. The resultant photonic structures combine the features of both relief- and phase-gratings. Selective cross-linking in polymer blend films based on different optical response of different molecular phases enabled “solidification” of the phase-separation scheme, providing a stable template for further photonic structuring. Dielectric and metallic structures are demonstrated for the fabrication methods using cross-linking in polymer films. Selective cross-linking enables direct patterning into polymer films without introducing additional fabrication procedures or additional materials. The diffraction processes of the emission of the patterned polymeric semiconductors may provide enhanced output coupling for light-emitting diodes or distributed feedback for lasers.

Box-like gel capsules from heterostructures based on a core-shell MOF as a template of crystal crosslinking.

Science.gov (United States)

Ishiwata, Takumi; Michibata, Ayano; Kokado, Kenta; Ferlay, Sylvie; Hosseini, Mir Wais; Sada, Kazuki

2018-02-06

New polymer capsules (PCs) were obtained using a crystal crosslinking (CC) method on core-shell MOF crystals. The latter are based on the epitaxial growth of two isostructural coordination polymers which are then selectively crosslinked. Decomposition of the non-reticulated phase leads to new PCs, possessing a well-defined hollow cubic shape reflecting the heterostructure of the template.

Investigation on the structure of temperature-responsive N-isopropylacrylamide microgels containing a new hydrophobic crosslinker

Directory of Open Access Journals (Sweden)

G. Roshan Deen

2015-12-01

Full Text Available Temperature-responsive poly(N-isopropylacrylamide microgels crosslinked with a new hydrophobic chemical crosslinker was prepared by surfactant-mediated precipitation emulsion polymerization. The temperature-responsive property of the microgel and the influence of the crosslinker on the swelling behaviour was studied systematically by light scattering and small-angle X-ray scattering (SAXS. The radius of gyration (Rg and the hydrodynamic radius (Rh of the microgels decreased with increase in temperature due to the volume-phase transition from a swollen to a collapsed state. The ratio of Rg/Rh below the transition temperature was lower than that of hard-spheres due to the lower crosslinking density of the microgels. The SAXS data were analysed by a model in which the microgels were modelled as core-shell particles with a graded interface. The model at intermediate temperatures included a central core and a more diffuse outer layer describing pending polymer chains with a low crosslinking density. In the fully swollen state, the microgels were modelled with a single component with a broad graded surface. In the collapsed state, they were modelled as homogeneous and relatively compact particles. The polymer volume fraction inside the microgel was also derived based on the model and was found to increase with increase in the temperature as a result of collapse of the microgel to compact particles. The polymer volume fraction in the core of the microgel in the collapsed state was about 60% which is higher than that of similar microgels crosslinked with hydrophilic and flexible crosslinkers.

Radiation-induced crosslinking of syndiotactic 1,2-polybutadiene

International Nuclear Information System (INIS)

Iwai, Tadashi; Hoshino, Sadao; Yamamoto, Rokuro; Okamoto, Hidemasa; Obana, Kazuyoshi.

1978-01-01

Crystalline syndiotactic 1, 2-polybutadiene (hereafter abbreviated as 1, 2-PB) developed in Ube Industries, Ltd. by its own technology is a new thermoplastic resin belonging to the intermediate region between rubber and plastics in its flexibility. By selecting appropriate catalyst composition, 1, 2-PB having the melting point of 90 to 200 deg. C and crystallization of 10 to 65% can be obtained. These 1, 2-PBs can be worked to formed products by general thermoplastic forming methods such as injection molding, extrusion forming and blow forming. Radiation-crosslinked 1, 2-PB changed to very hard polymers through heat treatment. This change has been found to be radical chain reaction of cyclic polymerization. The relation of radiation-induced crosslinking and thermal expansion behavior, and the changes of appearance and structural and physical properties with heat treatment of these polymers are described. That is, specific gravity has increased, tensile strength has been enhanced, and elongation has decreased. While dielectric strength and arc resistivity have been upgraded. Therefore, these polymers can be used for the following applications: food wrapping film, molded notions, molded low foaming material for the soles of footwears, highly foaming moldings such as sponges, electric insulation material such as cable coating and adhesives for many materials. It is considered that crosslinking contributes to the application to electric insulation materials and heat curing to heat-resistant materials and parts. (Wakatsuki, Y.)

Physical Characterization Of High Amylose/Pectin Mixtures Cross-Linked With Sodium Trimetaphosphate

International Nuclear Information System (INIS)

Carbinatto, F.M.; Cury, B.S.F.; Evangelista, R.C.

2010-01-01

Some researches have reported that pectin and high amylose mixtures presented superior mechanical properties in relation to those of the isolated polymers. In this work, mixtures at different ratios (1:4; 1:1) of pectin and high amylose were crosslinked with sodium trimetaphosphate at different degrees by varying reaction conditions. All samples were characterized by rheological and X-ray diffraction analyses. Samples without cross-linker were prepared as control. The oscillatory dynamic tests showed that all samples exhibited predominant elastic behavior, although cross-linked samples presented higher G' values, suggesting that crosslinking by phosphorylation resulted in more strength structures. The diffractograms showed that cross-linked samples underwent structural modifications that resulted in increase of crystallinity due to cross-linking process. (author)

On The improvement of physical and mechanical properties of PE by crosslinking

International Nuclear Information System (INIS)

Abbassi Souraki, F.; Morshedian, J.

2001-01-01

Improvement of PE properties has been carried out by several methods. In this work dicumyl peroxide was used for crosslinking of LDPE and bene improving the polymer properties. For sample preparation, an intensive mixing of polymer, peroxide and antioxidant in as Hake internal mixer at 110-115 d eg C was performed and followed by two-roll mixing. Finally process of crosslinking was conducted at 200 d eg C under 15 MPa pressure. After get content determination, tensile, DSc, DMTA and density tests were carried out on the samples. Results showed improved alterations in the properties

The Effect of Irradiation on Mechanical and Thermal Properties of Selected Types of Polymers

Directory of Open Access Journals (Sweden)

David Manas

2018-02-01

Full Text Available This article deals with the influence of electron-beam radiation on the micro-mechanical, thermo-mechanical, and structural properties of selected polymers. In the search for the desired improvement of polymers, it is possible to use, inter alia, one particular possible modification—Namely, crosslinking—Which is a process during which macromolecular chains start to connect to each other and, thus, create the spatial network in the structure. In the course of the treatment of the ionizing radiation, two actions can occur: crosslinking and scission of macromolecules, or degradation. Both these processes run in parallel. Using the crosslinking technology, standard and technical polymers can acquire the more “expensive” high-tech polymeric material properties and, thus, replace these materials in many applications. The polymers that were tested were selected from across the whole spectra of thermoplastics, ranging from commodity polymers, technical polymers, as well as high-performance polymers. These polymers were irradiated by different doses of beta radiation (33, 66, 99, 132, 165, and 198 kGy. The micro-mechanical and thermo-mechanical properties of these polymers were measured. When considering the results, it is obvious that irradiation acts on each polymer differently but, always when the optimal dose was found, the mechanical properties increased by up to 36%. The changes of micro-mechanical and thermo-mechanical properties were confirmed by structural measurement when the change of the micro-hardness and modulus corresponded to the crystalline phase change as determined by X-ray and gel content.

Synthesis of crosslinked poly (styrene-co-divinylbenzene-co ...

Indian Academy of Sciences (India)

Synthesis of crosslinked poly(styrene--divinylbenzene--sulfopropyl methacrylate) nanoparticles by emulsion polymerization: Tuning the particle size and surface charge density. Dhamodaran Arunbabu Mousumi Hazarika Somsankar Naik Tushar Jana. Polymers Volume 32 Issue 6 December 2009 pp 633-641 ...

Soft matter: rubber and networks

Science.gov (United States)

McKenna, Gregory B.

2018-06-01

Rubber networks are important and form the basis for materials with properties ranging from rubber tires to super absorbents and contact lenses. The development of the entropy ideas of rubber deformation thermodynamics provides a powerful framework from which to understand and to use these materials. In addition, swelling of the rubber in the presence of small molecule liquids or solvents leads to materials that are very soft and ‘gel’ like in nature. The review covers the thermodynamics of polymer networks and gels from the perspective of the thermodynamics and mechanics of the strain energy density function. Important relationships are presented and experimental results show that the continuum ideas contained in the phenomenological thermodynamics are valid, but that the molecular bases for some of them remain to be fully elucidated. This is particularly so in the case of the entropic gels or swollen networks. The review is concluded with some perspectives on other networks, ranging from entropic polymer networks such as thermoplastic elastomers to physical gels in which cross-link points are formed by glassy or crystalline domains. A discussion is provided for other physical gels in which the network forms a spinodal-like decomposition, both in thermoplastic polymers that form a glassy network upon phase separation and for colloidal gels that seem to have a similar behavior.

Solving the problem of building models of crosslinked polymers: an example focussing on validation of the properties of crosslinked epoxy resins.

Science.gov (United States)

Hall, Stephen A; Howlin, Brendan J; Hamerton, Ian; Baidak, Alex; Billaud, Claude; Ward, Steven

2012-01-01

The construction of molecular models of crosslinked polymers is an area of some difficulty and considerable interest. We report here a new method of constructing these models and validate the method by modelling three epoxy systems based on the epoxy monomers bisphenol F diglycidyl ether (BFDGE) and triglycidyl-p-amino phenol (TGAP) with the curing agent diamino diphenyl sulphone (DDS). The main emphasis of the work concerns the improvement of the techniques for the molecular simulation of these epoxies and specific attention is paid towards model construction techniques, including automated model building and prediction of glass transition temperatures (T(g)). Typical models comprise some 4200-4600 atoms (ca. 120-130 monomers). In a parallel empirical study, these systems have been cast, cured and analysed by dynamic mechanical thermal analysis (DMTA) to measure T(g). Results for the three epoxy systems yield good agreement with experimental T(g) ranges of 200-220°C, 270-285°C and 285-290°C with corresponding simulated ranges of 210-230°C, 250-300°C, and 250-300°C respectively.

Radiation polymerization and crosslinking of N-isopropylacrylamide in aqueous solution and in solid state

International Nuclear Information System (INIS)

Safranj, A.; Yoshida, Masaru; Omichi, Hideki; Nagaoka, Noriyasu; Kubota, Hitoshi; Katakai, Ryoichi.

1995-01-01

Poly(N-isopropylacrylamide) hydrogels were synthesized by radiation induced simultaneous polymerization and cross-linking. Aqueous monomer solutions and pure monomer, without crosslinker, were irradiated in nitrogen atmosphere at a 60 Co gamma source. The conversion from monomer to polymer and cross-linked gel was investigated as a function of temperature and monomer concentration. The swelling behavior of the gels showed clear dependence on the synthesis conditions. (author)

Sequential optimization of methotrexate encapsulation in micellar nano-networks of polyethyleneimine ionomer containing redox-sensitive cross-links

Directory of Open Access Journals (Sweden)

Abolmaali SS

2014-06-01

Full Text Available Samira Sadat Abolmaali,1 Ali Tamaddon,1,2 Gholamhossein Yousefi,1,2 Katayoun Javidnia,3 Rasoul Dinarvand41Department of Pharmaceutics, Shiraz School of Pharmacy, 2Center for Nanotechnology in Drug Delivery, 3Medicinal and Natural Products Chemistry Research Center, Shiraz University of Medical Sciences, Shiraz, Iran; 4Nanotechnology Research Centre, Faculty of Pharmacy, Tehran University of Medical Sciences, Tehran, IranAbstract: A functional polycation nanonetwork was developed for delivery of water soluble chemotherapeutic agents. The complexes of polyethyleneimine grafted methoxy polyethylene glycol (PEI-g-mPEG and Zn2+ were utilized as the micellar template for cross-linking with dithiodipropionic acid, followed by an acidic pH dialysis to remove the metal ion from the micellar template. The synthesis method was optimized according to pH, the molar ratio of Zn2+, and the cross-link ratio. The atomic force microscopy showed soft, discrete, and uniform nano-networks. They were sensitive to the simulated reductive environment as determined by Ellman's assay. They showed few positive ζ potential and an average hydrodynamic diameter of 162±10 nm, which decreased to 49±11 nm upon dehydration. The ionic character of the nano-networks allowed the achievement of a higher-loading capacity of methotrexate (MTX, approximately 57% weight per weight, depending on the cross-link and the drug feed ratios. The nano-networks actively loaded with MTX presented some suitable properties, such as the hydrodynamic size of 117±16 nm, polydispersity index of 0.22, and a prolonged swelling-controlled release profile over 24 hours that boosted following reductive activation of the nanonetwork biodegradation. Unlike the PEI ionomer, the nano-networks provided an acceptable cytotoxicity profile. The drug-loaded nano-networks exhibited more specific cytotoxicity against human hepatocellular carcinoma cells if compared to free MTX at concentrations above 1 µM. The

Densely crosslinked polycarbosiloxanes .2. Thermal and mechanical properties

NARCIS (Netherlands)

Flipsen, T.A C; Derks, R.; van der Vegt, H.A.; Stenekes, R.; Pennings, A.J; Hadziioannou, G

1997-01-01

The thermal and mechanical properties of two densely crosslinked polycarbosiloxane systems were investigated in relation to the molecular structure. The networks were prepared from functional branched prepolymers and crosslinked via a hydrosilylation curing reaction. The prepolymers having only

Mechanical reinforcement and segmental dynamics of polymer nanocomposites

Science.gov (United States)

Gong, Shushan

The addition of nanofiller into a polymer matrix will dramatically change the physical properties of polymer. The introduction of nanofiller makes the polymer more applicable in many industries, such as automobile tires, coatings, semiconductors, and packaging. The altered properties are not the simple combination of the characters from the two components. The interactions in polymer nanocomposites play an important role in determining the physical properties. This dissertation focuses on the mechanical properties of polymer nanocomposites (silica/poly-2-vinylpyridine) above their glass transition temperature Tg, as a model for automobile tires, which utilize small silica particles in crosslinked rubber far above Tg. We also investigate the impacts of the interaction between particle filler and polymer matrix on the altered mechanical properties. Dielectric relaxation spectroscopy (DRS) is used to study the glassy bound polymer layers formed around the particles. The results show evidence of the existence of immobilized polymer layers at the surface of each nanoparticle. At the same time, the thickness of the immobilized polymer layers is quantified and formed to be around 2 nm. Then we consider particles with glassy bound polymer layers are bridged together (either rubbery bridge or glassy bridge) by polymer chains and form small clusters. Clusters finally percolate to form a particle-polymer network as loading fraction increases. Rheology is used to study the network formation, and to predict the boundary of rubbery bridge and glassy bridge regimes. The distance between particles determines the type of polymer bridging. The particle spacing larger than Kuhn length makes flexible (rubbery) bridge with rheology described by a flexible Rouse model for percolation. When the spacing is shorter than the Kuhn length (~ 1nm), stiffer bridge forms instead, which is called glassy bridge. The mechanical differences between rubbery bridge and glassy bridge, and the effect of

Gas permeation through a polymer network

International Nuclear Information System (INIS)

Schmittmann, B; Gopalakrishnan, Manoj; Zia, R K P

2005-01-01

We study the diffusion of gas molecules through a two-dimensional network of polymers with the help of Monte Carlo simulations. The polymers are modelled as non-interacting random walks on the bonds of a two-dimensional square lattice, while the gas particles occupy the lattice cells. When a particle attempts to jump to a nearest-neighbour empty cell, it has to overcome an energy barrier which is determined by the number of polymer segments on the bond separating the two cells. We investigate the gas current J as a function of the mean segment density ρ, the polymer length l and the probability q m for hopping across m segments. Whereas J decreases monotonically with ρ for fixed l, its behaviour for fixed ρ and increasing ldepends strongly on q. For small, non-zero q, J appears to increase slowly with l. In contrast, for q = 0, it is dominated by the underlying percolation problem and can be non-monotonic. We provide heuristic arguments to put these interesting phenomena into context

Crosslinked Hexafluoropropylidene Polybenzimidazole Membranes with Chloromethyl Polysulfone for Fuel Cell Applications

DEFF Research Database (Denmark)

Yang, Jingshuai; Li, Qingfeng; Cleemann, Lars Nilausen

2013-01-01

Hexafluoropropylidene polybenzimidazole (F6PBI) was synthesized with excellent chemical stability and improved solubility. When doped with phosphoric acid, however, the F6PBI membranes showed plastic deformation at elevated temperatures. Further efforts were made to covalently crosslink F6PBI...... membranes with chloromethyl polysulfone as a polymeric crosslinker. Comparing with linear F6PBI and mPBI membranes, the polymer crosslinked F6PBI membranes exhibited little organo solubility, excellent stability towards the radical oxidation, high resistance to swelling in concentrated phosphoric acid...... with the linear F6PBI and mPBI membranes....

Electron beam irradiation crosslinked hydrogels based on tyramine conjugated gum tragacanth.

Science.gov (United States)

Tavakol, Moslem; Dehshiri, Saeedeh; Vasheghani-Farahani, Ebrahim

2016-11-05

In the present study, electron beam irradiation was applied to prepare a chemically crosslinked hydrogel based on tyramine conjugated gum tragacanth. Then, the gel content, swelling behavior and cytotoxicity of the hydrogels were evaluated. The gel content of the hydrogels was in the range of 75-85%. Equilibrium swelling degree of the hydrogels decreased from 51 to 14 with increasing polymer concentration and irradiation dose. Moisture retention capability of the hydrogels after 5h incubation at 37°C was in the range of 45-52 that is comparable with of commercial hydrogels. The cytotoxicity analysis showed the good biocompatibility of hydrogels. These results indicated that electron beam irradiation is a promising method to prepare chemically crosslinked tyramine conjugated gum tragacanth hydrogels for biomedical applications. Also, the versatility of electron beam irradiation for crosslinking of a variety of polymers possessing tyramine groups was demonstrated. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biohybrid Fibro-Porous Vascular Scaffolds: Effect of Crosslinking on Properties.

Science.gov (United States)

Thomas, Vinoy; Nozik, Danna; Patel, Harsh; Singh, Raj K; Vohra, Yogesh K

Tubular grafts were fabricated from blends of polycaprolactone (PCL) and poly(glycolide -co-caprolactone) (PGC) polymers and coated with an extracellular matrix containing collagens, laminin, and proteoglycans, but not growth factors (HuBiogel™). Multifunctional scaffolds from polymer blends and membrane proteins provide the necessary biomechanics and biological functions for tissue regeneration. Two crosslinking agents, a natural crosslinker namely genipin (Gp) and a carbodiimide reagent namely 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), were used for further stabilizing the protein matrix and the effect of crosslinking was evaluated for structural, morphological, mechanical properties using SEM, DSC and DMA. SEM images and fiber diameter distribution showed fiber-size between 0.2 µm to 1 µm with the majority of fiber diameters being under 500 nm, indicating upper range of protein fiber-sizes (for example, collagen fibers in extracellular matrix are in 50 to 500 nm diameter range). HB coating did not affect the mechanical properties, but increased its hydrophilicity of the graft. Overall data showed that PCL/PGC blends with 3:1 mass ratio exhibited mechanical properties comparable to those of human native arteries (tensile strength of 1-2 MPa and Young's modulus of crosslinking on coating stability was investigated to assure the retention of proteins on scaffold for effective cell-matrix interactions.

Fabrication and characterization of shape memory polymers at small-scales

Science.gov (United States)

Wornyo, Edem

The objective of this research is to thoroughly investigate the shape memory effect in polymers, characterize, and optimize these polymers for applications in information storage systems. Previous research effort in this field concentrated on shape memory metals for biomedical applications such as stents. Minimal work has been done on shape memory polymers; and the available work on shape memory polymers has not characterized the behaviors of this category of polymers fully. Copolymer shape memory materials based on diethylene glycol dimethacrylate (DEGDMA) crosslinker, and tert butyl acrylate (tBA) monomer are designed. The design encompasses a careful control of the backbone chemistry of the materials. Characterization methods such as dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC); and novel nanoscale techniques such as atomic force microscopy (AFM), and nanoindentation are applied to this system of materials. Designed experiments are conducted on the materials to optimize spin coating conditions for thin films. Furthermore, the recovery, a key for the use of these polymeric materials for information storage, is examined in detail with respect to temperature. In sum, the overarching objectives of the proposed research are to: (i) Design shape memory polymers based on polyethylene glycol dimethacrylate (PEGDMA) and diethylene glycol dimethacrylate (DEGDMA) crosslinkers, 2-hydroxyethyl methacrylate (HEMA) and tert-butyl acrylate monomer (tBA). (ii) Utilize dynamic mechanical analysis (DMA) to comprehend the thermomechanical properties of shape memory polymers based on DEGDMA and tBA. (iii) Utilize nanoindentation and atomic force microscopy (AFM) to understand the nanoscale behavior of these SMPs, and explore the strain storage and recovery of the polymers from a deformed state. (iv) Study spin coating conditions on thin film quality with designed experiments. (iv) Apply neural networks and genetic algorithms to optimize these systems.

Hydrophilic crosslinked-polymeric surface capable of effective suppression of protein adsorption

Energy Technology Data Exchange (ETDEWEB)

Kamon, Yuri; Inoue, Naoko; Mihara, Erika; Kitayama, Yukiya; Ooya, Tooru; Takeuchi, Toshifumi, E-mail: takeuchi@gold.kobe-u.ac.jp

2016-08-15

Highlights: • Three hydrophilic crosslinked polymers were examined for protein adsorption. • All polymers showed low nonspecific adsorption of negatively charged proteins. • Poly(MMPC) showed the lowest adsorption for positively charged proteins. • Poly(MMPC) is able to reduce nonspecific adsorption of a wide range of proteins. - Abstract: We investigated the nonspecific adsorption of proteins towards three hydrophilic crosslinked-polymeric thin layers prepared by surface-initiated atom transfer radical polymerization using N,N′-methylenebisacrylamide, 2-(methacryloyloxy)ethyl-[N-(2-methacryloyloxy)ethyl]phosphorylcholine (MMPC), or 6,6′-diacryloyl-trehalose crosslinkers. Protein binding experiments were performed by surface plasmon resonance with six proteins of different pI values including α-lactalbumin, bovine serum albumin (BSA), myoglobin, ribonuclease A, cytochrome C, and lysozyme in buffer solution at pH 7.4. All of the obtained crosslinked-polymeric thin layers showed low nonspecific adsorption of negatively charged proteins at pH 7.4 such as α-lactalbumin, BSA, and myoglobin. Nonspecific adsorption of positively charged proteins including ribonuclease A, cytochrome C, and lysozyme was the lowest for poly(MMPC). These results suggest poly(MMPC) can effectively reduce nonspecific adsorption of a wide range of proteins that are negatively or positively charged at pH 7.4. MMPC is a promising crosslinker for a wide range of polymeric materials requiring low nonspecific protein binding.

Shape memory polymers based on uniform aliphatic urethane networks

Energy Technology Data Exchange (ETDEWEB)

Wilson, T S; Bearinger, J P; Herberg, J L; Marion III, J E; Wright, W J; Evans, C L; Maitland, D J

2007-01-19

Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, in order to form amorphous networks with very uniform supermolecular structures which can be used as photo-thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N{prime},N{prime}-tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3-butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34 to 153 C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T{sub g}. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices.

Preparation and characterization of depolymerised chitosan films and crosslinked with sodium tripolyphosphate

International Nuclear Information System (INIS)

Salazar, Max Carlos; Valderrama Negron, Ana

2013-01-01

This work has studied the preparation and characterization of chitosan films (CS) crosslinked with sodium tripolyphosphate (TPP), prepared by the solvent evaporation method. Initially we studied the depolymerization of chitosan with sodium nitrite to get different polymer molecular weights in the used polymer. For example, we obtained chitosans of 554.22kDa and 133.37kDa of molecular weight. Afterward, prepared and characterized chitosans films crosslinked with TPP, evidently the hydrogen bridge interaction with the polyanion through IR, SEM, TG; also was performed swelling studies, with the objective of identified the type of kinetic model in which enable explain said phenomenon in these films. (author)

Radiation crosslinking of methylcellulose and hydroxyethylcellulose in concentrated aqueous solutions

International Nuclear Information System (INIS)

Wach, Radoslaw A.; Mitomo, Hiroshi; Nagasawa, Naotsugu; Yoshii, Fumio

2003-01-01

The effects of ionizing radiation on aqueous solutions of cellulose ethers, methylcellulose (MC) and hydroxyethylcellulose (HEC) were investigated. The well-established knowledge states that cellulose and its derivatives belong to degrading type of polymers. However, in our study intermolecular crosslinking initiated by gamma rays or electron beam leaded to the formation of insoluble gel. This is an opposite effect of irradiation to the degradation. Paste-like form of the initial specimen, i.e. concentration 20-30%, when water plasticizes the bulk of polymer; and a high dose rate were favorable for hydrogel formation. Gel fraction up to 60% and 70% was obtained from solutions of HEC and MC, respectively. Produced hydrogels swell markedly in aqueous media by imbibing and holding the solvent. Radiation parameters of irradiation, such as yields of degradation and crosslinking and the gelation dose, were evaluated by sol-gel analysis on the basis of Charlesby-Rosiak equation. Despite of the crosslinked structure, obtained hydrogels can be included into the group of biodegradable materials. They undergo decomposition by the action of cellulase enzyme or microorganisms from compost

New trends in radiation processing of polymers

International Nuclear Information System (INIS)

Chmielewski, Andrzej G.

2005-01-01

Nowadays, the modification of polymers covers radiation cross-linking, radiation induced polymerization (graft polymerization and curing) and the degradation of polymers. The success of radiation technology for the processing of synthetic polymers can be attributed to two reasons, namely the easiness of processing in various shapes and sizes and, secondly, most of these polymers undergo cross-linking reaction upon exposure to radiation. years, natural polymers are being looked at again with renewed interest because of their unique characteristics like inherent biocompatibility, biodegradability and easy availability. However the recent progress in the field regards development of new processing methods and technical solutions. No other break trough technologies or products based on synthetic polymers are reported recently. The future progress, both from scientific and practical points of view, concerns nanotechnology and natural polymer processing. Overview of the subject, including the works performed in the Institute of the author is presented in the paper. (author)

Theoretical studies of ionic conductivity of crosslinked chitosan membranes

Energy Technology Data Exchange (ETDEWEB)

Chavez, Ernesto Lopez [Programa de Ingenieria Molecular y Nuevos Materiales, Universidad Autonoma de la Ciudad de Mexico, Fray Servando Teresa de Mier 92, 1er. Piso, Col Centro, Mexico D.F. CP 06080 (Mexico); Oviedo-Roa, R.; Contreras-Perez, Gustavo; Martinez-Magadan, Jose Manuel [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas Norte 152, Col. San Bartolo Atepehuacan, CP 07730 Mexico D.F. (Mexico); Castillo-Alvarado, F.L. [Escuela Superior de Fisica y Matematicas del Instituto Politecnico Nacional, Edificio 9 de la UPALM, Colonia Lindavista, Mexico D.F. CP 07738 (Mexico)

2010-11-15

Ionic conductivity of crosslinked chitosan membranes was studied using techniques of molecular modeling and simulation. The COMPASS force field was used. The simulation allows the description of the mechanism of ionic conductivity along the polymer matrix. The theoretical results obtained are compared with experimental results for chitosan membranes. The analysis suggests that the conduction mechanism is portrayed by the overlapping large Polaron tunneling model. In addition, when the chitosan membrane was crosslinked with an appropriate degree of crosslinking its ionic conductivity, at room temperature, was increased by about one order of magnitude. The chitosan membranes can be used as electrolytes in solid state batteries, electric double layer capacitors and fuel cells. (author)

A Study of Functional Polymer Colloids Prepared Using Thiol-Ene/Yne Click Chemistry

Science.gov (United States)

Durham, Olivia Z.

This project demonstrates the first instance of thiol-ene chemistry as the polymerization method for the production of polymer colloids in two-phase heterogeneous suspensions, miniemulsions, and emulsions. This work was also expanded to thiol-yne chemistry for the production of polymer particles containing increased crosslinking density. The utility of thiol-ene and thiol-yne chemistries for polymerization and polymer modification is well established in bulk systems. These reactions are considered 'click' reactions, which can be defined as processes that are both facile and simple, offering high yields with nearly 100% conversion, no side products, easy product separation, compatibility with a diverse variety of commercially available starting materials, and orthogonality with other chemistries. In addition, thiol-ene and thiol-yne chemistry follow a step-growth mechanism for the development of highly uniform polymer networks, where polymer growth is dependent on the coupling of functional groups. These step-growth polymerization systems are in stark contrast to the chain-growth mechanisms of acrylic and styrenic monomers that have dominated the field of conventional heterogeneous polymerizations. Preliminary studies evaluated the mechanism of particle production in suspension and miniemulsion systems. Monomer droplets were compared to the final polymer particles to confirm that particle growth occurred through the polymerization of monomer droplets. Additional parameters examined include homogenization energy (mechanical mixing), diluent species and concentration, and monomer content. These reactions were conducted using photoinitiation to yield particles in a matter of minutes with diameters in the size range of several microns to hundreds of microns in suspensions or submicron particles in miniemulsions. Improved control over the particle size and size distribution was examined through variation of reaction parameters. In addition, a method of seeded suspension

State of the water in crosslinked sulfonated poly(ether ether ketone). Two-dimensional differential scanning calorimetry correlation mapping

Energy Technology Data Exchange (ETDEWEB)

Al Lafi, Abdul G. [Department of Chemistry, Atomic Energy Commission, Damascus, P.O. Box 6091 (Syrian Arab Republic); Hay, James N., E-mail: cscientific9@aec.org.sy [The School of Metallurgy and Materials, College of Physical Sciences and Engineering, University of Birmingham, Edgbaston, Birmingham B15 2TT (United Kingdom)

2015-07-20

Highlights: • 2D-DSC mapping was applied to analyze the heat flow responses of hydrated crosslinked sPEEK. • Two types of loosely bond water were observed. • The first was bond to the sulfonic acid groups and increased with ion exchange capacity. • The second was attributed to the polar groups introduced by ions irradiation and increased with crosslinking degree. • DSC combined with 2D mapping provides a powerful tool for polymer structural determination. - Abstract: This paper reports the first application of two-dimensional differential scanning calorimetry correlation mapping, 2D-DSC-CM to analyze the heat flow responses of sulphonated poly(ether ether ketone), sPEEK, films having different ion exchange capacity and degrees of crosslinks. With the help of high resolution and high sensitivity of 2D-DSC-CM, it was possible to locate two types of loosely bound water within the structure of crosslinked sPEEK. The first was bound to the sulfonic acid groups and dependent on the ion exchange capacity of the sPEEK. The second was bound to other polar groups, either introduced by irradiation with ions and dependent on the crosslinking degree or present in the polymer such as the carbonyl groups or terminal units. The results suggest that the ability of the sulfonic acid groups in the crosslinked sPEEK membranes to adsorb water molecules is increased by crosslinking, probably due to the better close packing efficiency of the crosslinked samples. DSC combined with 2D correlation mapping provides a fast and powerful tool for polymer structural determination.

Thiol-ene reaction as tool for crosslinking of polynorbornene micelles in the nanoscale

Science.gov (United States)

Rupp, Barbara; Bauer, Thomas; Slugovc, Christian

2009-08-01

The thiol-ene reaction is a established photoreaction of multifunctional thiols and enes. Virtually any type of ene will participate in a free radical polymerisation process with a thiol. An advantage over many other photochemical reactions is that the reaction proceeds almost as rapidly in ambient conditions as in inert atmosphere. In this work we introduce the UV-crosslinking of polynorbornenes made by ring opening metathesis polymerization making use of the residual double bond in the polymer backbone. The crosslinking experiments were done in thin films and were followed by FTIR measurements, to proof the accessibility of double-bonds in the polymers for the addition of the thiols. As a result of these pre-experiments we created flexible and light transmitting films. To further increase the scope of this reaction, amphiphilic block copolymers were prepared and used to form block copolymer micelles in a selective solvent, which were subsequently crosslinked with pentaerythritol tetra(3-mercaptopropionate) (PETMP). FT-IR, DLS and SEM-measurements were used to prove the successful crosslinking and thus nanoparticle formation.

In Situ Forming, Cytocompatible, and Self-Recoverable Tough Hydrogels Based on Dual Ionic and Click Cross-Linked Alginate.

Science.gov (United States)

Ghanian, Mohammad Hossein; Mirzadeh, Hamid; Baharvand, Hossein

2018-05-14

A dual cross-linking strategy was developed to answer the urgent need for fatigue-resistant, cytocompatible, and in situ forming tough hydrogels. Clickable, yet calcium-binding derivatives of alginate were synthesized by partial substitution of its carboxyl functionalities with furan, which could come into Diels-Alder click reaction with maleimide end groups of a four arm poly(ethylene glycol) cross-linker. Tuning the cooperative viscoelastic action of transient ionic and permanent click cross-links within the single network of alginate provided a soft tough hydrogel with a set of interesting features: (i) immediate self-recovery under cyclic loading, (ii) highly efficient and autonomous self-healing upon fracture, (iii) in situ forming ability for molding and minimally invasive injection, (iv) capability for viable cell encapsulation, and (v) reactivity for on-demand biomolecule conjugation. The facile strategy is applicable to a wide range of natural and synthetic polymers by introducing the calcium binding and click reacting functional groups and can broaden the use of tough hydrogels in load-bearing, cell-laden applications such as soft tissue engineering and bioactuators.

Crosslinking of epoxy-oligoesteric mixtures in the presence of dioxydiphenylpropane diglycidyl ether modified with adipic acid

Czech Academy of Sciences Publication Activity Database

Bratychak, M.; Zubal, O.; Bashta, Bogdana; Ivashkiv, O.; Shyshchak, O.; Haponiuk, J.

2017-01-01

Roč. 11, č. 2 (2017), s. 180-187 ISSN 1996-4196 Institutional support: RVO:61389013 Keywords : crosslinking * polymer films * epoxy resin Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science

Radiation induced crosslinking of polytetrafluoroethylene

International Nuclear Information System (INIS)

Oshima, Akihiro; Tabata, Yoneho; Ikeda, Shigetoshi; Otsuhata, Kazushige; Kudoh, Hisaaki; Seguchi, Tadao.

1995-01-01

The Irradiation temperature effect on polytetrafluoroethylene (PTFE) from room temperature to 380degC was investigated by tensile test and thermal analysis. The behavior of tensile properties and changes of crystallinity on irradiation indicated the formation of a network structure in PTFE by radiation induced crosslinking in inert gas in the molten state just above the melting temperature of PTFE (327degC). The crosslinked PTFE showed a much improved radiation resistance in an atmospheric radiation field. (author)

Synthesis of fish scales gelatin-chitosan crosslinked films by gamma irradiation techniques

International Nuclear Information System (INIS)

Erizal; Perkasa, D.P.; Abbas, B.; Sulistioso, G.S.

2013-01-01

Gelatin is an important component of fish scales. Nowadays, attention has increased concerning the application of gelatin.The aim of this research was to improve the mechanical properties of gelatin produced from fish scales, which concurrently could increase the usefulness of fish scales. Gelatin (G) is prone to degrade or dissolve in water at room temperature, therefore to enhance its lifetime, it has to be modified with other compound such as chitosan. Chitosan (Cs) is a biodegradable polymer, which has biocompatibility and antibacterial properties. In this study, gelatin solution was mixed with chitosan solution in various ratios (G/Cs: 100/0, 75/25, 50/50, 25/75, 0/100), casted at room temperature to make composite films, then tested for the effectiveness of various gamma irradiation doses (10-40 kGy) for crosslinking of the two polymers. Chemical changes of the films were measured by FT-IR, gel fractions were determined by gravimetry, and mechanical properties were determined by tensile strength and elongation at break using universal testing machine. At optimum conditions ( 30 kGy and 75% Cs), the gel fraction, tensile strength, and elongation at break were higher leading to a stronger composite films as compared to the gelatin film. FTIR spectral analysis showed that gelatin and chitosan formed a crosslinked network. It was concluded that G-Cs films prepared by gamma irradiation have improved their mechanical properties than the gelatin itself. (author)

Graphene oxide-based benzimidazole-crosslinked networks for high-performance supercapacitors

Science.gov (United States)

Cui, Yi; Cheng, Qian-Yi; Wu, Haiping; Wei, Zhixiang; Han, Bao-Hang

2013-08-01

The synthesis of graphene oxide (GO)-based benzimidazole-crosslinked network (GOBIN) materials is presented. These materials are prepared by the covalent crosslinking of GO sheets using a condensation reaction between the carboxylic acid moieties on the GO surface and the o-aminophenyl end groups of 3,3'-diaminobenzidine (or 1,2,4,5-benzenetetraamine tetrahydrochloride). An efficient one-pot catalyst- and template-free synthesis was performed. The obtained porous GO-based materials possess a Brunauer-Emmett-Teller specific surface area ranging from 260 to 920 m2 g-1. Electrochemical testing indicates that the GOBIN materials display a specific capacitance up to 370 F g-1 at a current density of 0.1 A g-1 and about 90% of the original capacitance is retained after 5000 cycles at a current density of 3 A g-1. Therefore, GOBIN materials can be employed as promising electrode materials for high-performance supercapacitors with outstanding cycling stability. Furthermore, owing to their significantly high specific surface area, these materials also show hydrogen uptake (up to 1.24 wt%, at 77 K and 1.0 bar) and carbon dioxide capture (up to 14.2 wt%, at 273 K and 1.0 bar) properties. As a result, these GO-based porous materials improve both the supercapacitor performance and gas sorption property, which demonstrate an excellent performance in the practical application of energy storage.The synthesis of graphene oxide (GO)-based benzimidazole-crosslinked network (GOBIN) materials is presented. These materials are prepared by the covalent crosslinking of GO sheets using a condensation reaction between the carboxylic acid moieties on the GO surface and the o-aminophenyl end groups of 3,3'-diaminobenzidine (or 1,2,4,5-benzenetetraamine tetrahydrochloride). An efficient one-pot catalyst- and template-free synthesis was performed. The obtained porous GO-based materials possess a Brunauer-Emmett-Teller specific surface area ranging from 260 to 920 m2 g-1. Electrochemical testing

AFM and SFG studies of pHEMA-based hydrogel contact lens surfaces in saline solution: adhesion, friction, and the presence of non-crosslinked polymer chains at the surface.

Science.gov (United States)

Kim, Seong Han; Opdahl, Aric; Marmo, Chris; Somorjai, Gabor A

2002-04-01

The surfaces of two types of soft contact lenses neutral and ionic hydrogels--were characterized by atomic force microscopy (AFM) and sum-frequency-generation (SFG) vibrational spectroscopy. AFM measurements in saline solution showed that the presence of ionic functional groups at the surface lowered the friction and adhesion to a hydrophobic polystyrene tip. This was attributed to the specific interactions of water and the molecular orientation of hydrogel chains at the surface. Friction and adhesion behavior also revealed the presence of domains of non-crosslinked polymer chains at the lens surface. SFG showed that the lens surface became partially dehydrated upon exposure to air. On this partially dehydrated lens surface, the non-crosslinked domains exhibited low friction and adhesion in AFM. Fully hydrated in saline solution, the non-crosslinked domains extended more than tens of nanometers into solution and were mobile.

Modelling the permeability of polymers: a neural network approach

NARCIS (Netherlands)

Wessling, Matthias; Mulder, M.H.V.; Bos, A.; Bos, A.; van der Linden, M.K.T.; Bos, M.; van der Linden, W.E.

1994-01-01

In this short communication, the prediction of the permeability of carbon dioxide through different polymers using a neural network is studied. A neural network is a numeric-mathematical construction that can model complex non-linear relationships. Here it is used to correlate the IR spectrum of a

Modeling fiber Bragg grating device networks in photomechanical polymer optical fibers

Science.gov (United States)

Lanska, Joseph T.; Kuzyk, Mark G.; Sullivan, Dennis M.

2015-09-01

We report on the modeling of fiber Bragg grating (FBG) networks in poly(methyl methacrylate) (PMMA) polymer fibers doped with azo dyes. Our target is the development of Photomechanical Optical Devices (PODs), comprised of two FBGs in series, separated by a Fabry-Perot cavity of photomechanical material. PODs exhibit photomechanical multi-stability, with the capacity to access multiple length states for a fixed input intensity when a mechanical shock is applied. Using finite-difference time-domain (FDTD) numerical methods, we modeled the photomechanical response of both Fabry-Perot and Bragg-type PODs in a single polymer optical fiber. The polymer fiber was modeled as an instantaneous Kerr-type nonlinear χ(3) material. Our model correctly predicts the essential optical features of FBGs as well as the photomechanical multi-stability of nonlinear Fabry-Perot cavity-based PODs. Networks of PODs may provide a framework for smart shape-shifting materials and fast optical computation where the decision process is distributed over the entire network. In addition, a POD can act as memory, and its response can depend on input history. Our models inform and will accelerate targeted development of novel Bragg grating-based polymer fiber device networks for a variety of applications in optical computing and smart materials.

The Effect of Polymer Molecular Weight on Citrate Crosslinked ...

African Journals Online (AJOL)

Erah

Purpose: To develop citrate crosslinked chitosan films using chitosan of different molecular weights. (MW) in .... left to stand until trapped air bubbles ... blotted out carefully with filter paper from the .... potential as biodegradable stent coatings. J.

Tensile and fracture behavior of polymer foams

International Nuclear Information System (INIS)

Kabir, Md. E.; Saha, M.C.; Jeelani, S.

2006-01-01

Tensile and mode-I fracture behavior of cross-linked polyvinyl chloride (PVC) and rigid polyurethane (PUR) foams are examined. Tension tests are performed using prismatic bar specimens and mode-I fracture tests are performed using single edge notched bend (SENB) specimens under three-point bending. Test specimens are prepared from PVC foams with three densities and two different levels of cross-linking, and PUR foam with one density. Tension and quasi-static fracture tests are performed using a Zwick/Rowell test machine. Dynamic fracture tests are performed using a DYNATUP model 8210 instrumented drop-tower test set up at three different impact energy levels. Various parameters such as specimen size, loading rate, foam density, cross-linking, crack length, cell orientation (flow and rise-direction) and solid polymer material are studied. It is found that foam density and solid polymer material have a significant effect on tensile strength, modulus, and fracture toughness of polymer foams. Level of polymer cross-linking is also found to have a significant effect on fracture toughness. The presence of cracks in the rise- and flow direction as well as loading rate has minimal effect. Dynamic fracture behavior is found to be different as compared to quasi-static fracture behavior. Dynamic fracture toughness (K d ) increases with impact energy. Examination of fracture surfaces reveals that the fracture occurs in fairly brittle manner for all foam materials

Solvent-resistant organic transistors and thermally stable organic photovoltaics based on cross-linkable conjugated polymers

KAUST Repository

Kim, Hyeongjun

2012-01-10

Conjugated polymers, in general, are unstable when exposed to air, solvent, or thermal treatment, and these challenges limit their practical applications. Therefore, it is of great importance to develop new materials or methodologies that can enable organic electronics with air stability, solvent resistance, and thermal stability. Herein, we have developed a simple but powerful approach to achieve solvent-resistant and thermally stable organic electronic devices with a remarkably improved air stability, by introducing an azide cross-linkable group into a conjugated polymer. To demonstrate this concept, we have synthesized polythiophene with azide groups attached to end of the alkyl chain (P3HT-azide). Photo-cross-linking of P3HT-azide copolymers dramatically improves the solvent resistance of the active layer without disrupting the molecular ordering and charge transport. This is the first demonstration of solvent-resistant organic transistors. Furthermore, the bulk-heterojunction organic photovoltaics (BHJ OPVs) containing P3HT-azide copolymers show an average efficiency higher than 3.3% after 40 h annealing at an elevated temperature of 150 °C, which represents one of the most thermally stable OPV devices reported to date. This enhanced stability is due to an in situ compatibilizer that forms at the P3HT/PCBM interface and suppresses macrophase separation. Our approach paves a way toward organic electronics with robust and stable operations. © 2011 American Chemical Society.

Modeling interacting dynamic networks: II. Systematic study of the statistical properties of cross-links between two networks with preferred degrees

International Nuclear Information System (INIS)

Liu, Wenjia; Schmittmann, B; Zia, R K P

2014-01-01

In a recent work (Liu et al, 2013 J. Stat. Mech. P08001), we introduced dynamic networks with preferred degrees and presented simulation and analytic studies of a single, homogeneous system as well as two interacting networks. Here, we extend these studies to a wider range of parameter space, in a more systematic fashion. Though the interaction we introduced seems simple and intuitive, it produced dramatically different behavior in the single- and two-network systems. Specifically, partitioning the single network into two identical sectors, we find the cross-link distribution to be a sharply peaked Gaussian. In stark contrast, we find a very broad and flat plateau in the case of two interacting identical networks. A sound understanding of this phenomenon remains elusive. Exploring more asymmetric interacting networks, we discover a kind of ‘universal behavior’ for systems in which the ‘introverts’ (nodes with smaller preferred degree) are far outnumbered. Remarkably, an approximation scheme for their degree distribution can be formulated, leading to very successful predictions. (paper)

Temperature range extension of an organically crosslinked polymer system and its successful field application for water and gas shutoff

Energy Technology Data Exchange (ETDEWEB)

Vasquez, Julio; Eoff, Larry; Dalrymple, Dwyann [Halliburton, Rio de Janeiro. RJ (Brazil)

2008-07-01

Excessive water production from hydrocarbon reservoirs is one of the most serious problems in the oil industry. Water production greatly affects the economic life of producing wells and brings along secondary problems such as sand production, corrosion, and tubular scale. Remediation techniques for controlling water production, generally referred to as conformance control, include the use of polymer systems to reduce or plug permeability to water. This paper presents the laboratory evaluation of an organically crosslinked polymer (OCP) system used as a sealant for water control problems in hydrocarbon wells. Originally, the OCP system had a limited working temperature range (140 deg to 260 deg F). Recently, an alternative base polymer (for low temperatures) and a retarder (for high temperatures) have been introduced to expand the temperature range of applicability of the OCP system from 70 deg F to 350 deg F without compromising its effectiveness or thermal stability. More than 400 jobs have been performed with the OCP system around the world to address conformance problems such as water coning/cresting, high-permeability streaks, gravel pack isolation, fracture shutoff, and casing leak repairs. This paper presents an overview of case histories that used the OCP system in various regions of the world for a wide variety of applications. (author)

PDMS Network Structure-Property Relationships: Influence of Molecular Architecture on Mechanical and Wetting Properties

Science.gov (United States)

Melillo, Matthew Joseph

Poly(dimethylsiloxane) (PDMS) is one of the most common elastomers, with applications ranging from sealants and marine-antifouling coatings to medical devices and absorbents for water treatment. Fundamental understanding of how liquids spread on the surface of and absorb into and leach out of PDMS networks is of critical importance for the design and use in another application - microfluidic devices. The growing use of PDMS in microfluidic devices raises the concern that some researchers may use this material without fully understanding all of its advantages, drawbacks, and intricacies. The primary goal of this Ph.D. dissertation is to elucidate PDMS network molecular structure to macroscopic property relationships and to demonstrate how molecular architecture can alter dynamic mechanical and wetting characteristics. We prepare PDMS materials by using vinyl/ tetrakis(dimethylsiloxy)silane (TDSS) and silanol/ tetraethylorthosilicate (TEOS) combinations of PDMS end-groups and crosslinkers as two model systems. Under constant curing conditions, we systematically study the effects of polymer molecular weight, loading of crosslinker, and end-group chemical functionality on the extent of gelation and the dynamic mechanical and water wetting properties of end-linked PDMS networks. The extent of the gelation reaction is determined using the Soxhlet extraction to quantify the amount of material that did and did not participate in the crosslinking reactions, termed the gel and sol fractions, respectively. We use the Miller-Macosko model in conjunction with the gel fraction and precise chemical composition (i.e., stoichiometric ratio and molecular weight) to determine the fractions of elastic and pendant material, the molecular weight between chemical crosslinks, and the average effective functionality of the crosslinker molecule. Based on dynamic mechanical testing, we find that the maximum storage moduli are achieved at optimal stoichiometric conditions in the vinyl

Radiation Modification of Some Natural Polymers and Their Potential Applications

International Nuclear Information System (INIS)

Refaee, A.M.E.A.

2012-01-01

(PAAm) which is one of the most popular polymers used to reduce water runoff and increase infiltration rates in field agricultural applications. There are different methods to improve water holding capacity of PAAm among of them; adjusting the density of its crosslinking network structure. Radiation technique is promising for preparation of hydrogels because a polymer in aqueous solution or in the water swollen state readily undergoes crosslinking on irradiation to yield a gel-like material. Irradiation dose can control the crosslinking yield of polymer. Addition of few amount of degraded natural polymer during the irradiation processing of PAAm can also reduce the hydrogel network structural density and influences its water holding capacity. Moreover, the low molecular weight natural polymer like alginate or chitosan incorporated in PAAm hydrogel help in promoting the plant growth when such hydrogels used as water supplied soil conditioner. In this connection, the crosslinked copolymers of γ-rays degraded alginate, chitosan or both of them with PAAm were prepared using ionizing radiation. The preparation conditions of the polyacrylamide/alginate (PAAm/Alg), polyacrylamide/chitosan (PAAm/CS) and polyacrylamide/alginate/chitosan (PAAm/Alg/CS) crosslinked hydrogels, such as the effect of the irradiation dose and the copolymer composition on the matrix gel content and water absorbency will be studied. The effect of different types of cations or fertilizers or buffers of different pH's on water absorbency of prepared hydrogels will be investigated. The possible use of such copolymer hydrogels in the field of agriculture for some plants will be investigated.

Solving the problem of building models of crosslinked polymers: an example focussing on validation of the properties of crosslinked epoxy resins.

Directory of Open Access Journals (Sweden)

Stephen A Hall

Full Text Available The construction of molecular models of crosslinked polymers is an area of some difficulty and considerable interest. We report here a new method of constructing these models and validate the method by modelling three epoxy systems based on the epoxy monomers bisphenol F diglycidyl ether (BFDGE and triglycidyl-p-amino phenol (TGAP with the curing agent diamino diphenyl sulphone (DDS. The main emphasis of the work concerns the improvement of the techniques for the molecular simulation of these epoxies and specific attention is paid towards model construction techniques, including automated model building and prediction of glass transition temperatures (T(g. Typical models comprise some 4200-4600 atoms (ca. 120-130 monomers. In a parallel empirical study, these systems have been cast, cured and analysed by dynamic mechanical thermal analysis (DMTA to measure T(g. Results for the three epoxy systems yield good agreement with experimental T(g ranges of 200-220°C, 270-285°C and 285-290°C with corresponding simulated ranges of 210-230°C, 250-300°C, and 250-300°C respectively.

Triazine containing N-rich microporous organic polymers for CO2 capture and unprecedented CO2/N2 selectivity

International Nuclear Information System (INIS)

Bhunia, Subhajit; Bhanja, Piyali; Das, Sabuj Kanti; Sen, Tapas; Bhaumik, Asim

2017-01-01

Targeted synthesis of microporous adsorbents for CO 2 capture and storage is very challenging in the context of remediation from green house gases. Herein we report two novel N-rich microporous networks SB-TRZ-CRZ and SB-TRZ-TPA by extensive incorporation of triazine containing tripodal moiety in the porous polymer framework. These materials showed excellent CO 2 storage capacities: SB-TRZ-CRZ displayed the CO 2 uptake capacity of 25.5 wt% upto 1 bar at 273 K and SB-TRZ-TPA gave that of 16 wt% under identical conditions. The substantial dipole quadruple interaction between network (polar triazine) and CO 2 boosts the selectivity for CO 2 /N 2 . SB-TRZ-CRZ has this CO 2 /N 2 selectivity ratio of 377, whereas for SB-TRZ-TPA it was 97. Compared to other porous polymers, these materials are very cost effective, scalable and very promising material for clean energy application and environmental issues. - Graphical abstract: We report two novel N-rich microporous polymeric materials by doping of triazine containing tripodal dopant in the organic framework. These materials showed excellent CO 2 storage capacities as high as 25.5 wt% under 1 bar pressure with exceptional CO 2 /N 2 selectivity of 377. - Highlights: • Triazine containing trimodal moiety incorporated in polycarbazolic and poly triphenylamine networks. • N-rich crosslinked polymers with high BET surface area and 1.5–1.7 nm size large micropores. • CO 2 uptake capacity of 25.5 wt% upto 1 bar at 273 K. • These crosslinked porous polymers showed exceptional CO 2 /N 2 selectivity.

Cross-Linked Poly(vinylidene fluoride-co-hexafluoropropene (PVDF-co-HFP Gel Polymer Electrolyte for Flexible Li-Ion Battery Integrated with Organic Light Emitting Diode (OLED

Directory of Open Access Journals (Sweden)

Ilhwan Kim

2018-04-01

Full Text Available Here, we fabricate poly(vinylidene fluoride-co-hexafluoropropene (PVDF-co-HFP by electrospinning for a gel polymer electrolyte (GPE for use in flexible Li-ion batteries (LIBs. As a solvent, we use N-methyl-2-pyrrolidone (NMP, which helps produce the cross-linked morphology of PVDF-co-HFP separator, owing to its low volatility. The cross-linked PVDF-co-HFP separator shows an uptake rate higher than that of a commercialized polypropylene (PP separator. Moreover, the PVDF-co-HFP separator shows an ionic conductivity of 2.3 × 10−3 S/cm at room temperature, comparable with previously reported values. An LIB full-cell assembled with the PVDF-co-HFP-based GPE shows capacities higher than its counterpart with the commercialized PP separator, confirming that the cross-linked PVDF-co-HFP separator provides highly efficient ionic conducting pathways. In addition, we integrate a flexible LIB cell using the PVDF-co-HFP GPE with a flexible organic light emitting diode (OLED, demonstrating a fully flexible unit of LIB and OLED.

The Effect of Polymer Molecular Weight on Citrate Crosslinked ...

African Journals Online (AJOL)

SEM), dissolution studies and differential scanning calorimetry (DSC) for surface ... Conclusion: The citrate-crosslinked chitosan films can be modulated to vary swelling and drug release at pH 3.5 and 6.2; this feature makes them useful tools for ...

Metal Catalysis with Nanostructured Metals Supported Inside Strongly Acidic Cross-linked Polymer Frameworks: Influence of Reduction Conditions of AuIII-containing Resins on Metal Nanoclusters Formation in Macroreticular and Gel-Type Materials

Czech Academy of Sciences Publication Activity Database

Calore, L.; Cavinato, g.; Canton, P.; Peruzzo, L.; Banavali, R.; Jeřábek, Karel; Corain, B.

2012-01-01

Roč. 391, AUG 30 (2012), s. 114-120 ISSN 0020-1693 Institutional support: RVO:67985858 Keywords : strongly acidic cross-linked polymer * frameworks * gold(0) nanoclusters Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 1.687, year: 2012

A Review on Recent Advances in Stabilizing Peptides/Proteins upon Fabrication in Hydrogels from Biodegradable Polymers

OpenAIRE

Faisal Raza; Hajra Zafar; Ying Zhu; Yuan Ren; Aftab -Ullah; Asif Ullah Khan; Xinyi He; Han Han; Md Aquib; Kofi Oti Boakye-Yiadom; Liang Ge

2018-01-01

Hydrogels evolved as an outstanding carrier material for local and controlled drug delivery that tend to overcome the shortcomings of old conventional dosage forms for small drugs (NSAIDS) and large peptides and proteins. The aqueous swellable and crosslinked polymeric network structure of hydrogels is composed of various natural, synthetic and semisynthetic biodegradable polymers. Hydrogels have remarkable properties of functionality, reversibility, sterilizability, and biocompatibility. All...

Mechanocatalytic polymerization and cross-linking in a polymeric matrix

NARCIS (Netherlands)

Jakobs, R.T.M.; Ma, Shuang; Sijbesma, R.P.

2013-01-01

A latent olefin metathesis catalyst, bearing two polymeric NHC ligands, was embedded in a semicrystalline polymer matrix containing cyclic olefins. The catalyst was activated by straining the solid material under compression, resulting in polymerization and cross-linking reactions of the monomers in