989 resultados para Poly(dimethylsiloxane) Networks
Resumo:
The effects of solvent nature on the surface topographies of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blend films spin-coated onto the silicon wafer were investigated. Four different solvents, such as ethylbenzene, toluene, tetrahydrofuran and dichloromethane, were chosen. They are better solvents for PS than that for PMMA. When dichloromethane, tetrahydrofuran and toluene were used, PMMA-rich phase domains protruded from the background of PS. When ethylbenzene was used, PS-rich phase domains elevated on the average height of PMMA-rich phase domains. In addition, continuous pits, networks and isolated droplets consisted of PS formed on the blend film surfaces with the decrease of polymer concentrations. The mechanism of the surface morphology evolution was discussed in detail.
Resumo:
Conducting polyaniline-poly(ethylene oxide) blends were prepared from their aqueous solutions. The blends displayed an electrical conductivity percolation threshold as low as 1.83 wt % of polyaniline loading. As demonstrated by scanning electron microscopy, polarized optical microscopy, and wide-angle X-ray diffraction studies, the conducting polyaniline took a fibrillar morphology in the blend, and it existed only in the amorphous phase of poly(ethylene oxide). A three-phase model combining morphological factors instead of a two-phase model was proposed to explain the low-conductivity percolation threshold.
Resumo:
Poly(ethylene oxide) (PEO) and silica (SiO2) organic-inorganic hybrid materials have been synthesized by sol-gel approach. The crystallization behavior of PEO in silica networks has been investigated by differential scanning calorimeter (DSC) and scanning electron micrograph (SEM). The degree of PEO crystallinity in PEO/SiO2 hybrid networks reduces with the increase of SiO2. PEO is in amorphous state when the concentration of PEO is lower than 50 wt% in the hybrid materials. The melting points of PEO in the networks are lower than that of pure PEG, but the melting point of PEO in the networks almost has the same melting point. WAXD and SEM results show that the crystalline behavior of PEO in PEO/SiO2 hybrid system is sternly confined. (C) 1999 Elsevier Science Ltd. All rights reserved.
Resumo:
Poly (ethylene oxide) (PEO) and poly (trimethopropane trimethacrylate) (PTMPTMA) interpenetrate networks have been synthesized. The confined crystallization behavior of PEO in the PTMTYTMA networks has been investigated by a differential scanning calorimeter and scanning electron microscope. The degree of PEO crystallinity in PEO/PTMPTMA interpenetrate networks reduces with the increase of PTMPTMA. PEO is in an amorphous state when the concentration of PEO is lower than 50% in the interpenetrate networks system. The melting points of crystalline PEO in the networks are lower than that of pure PEG, and the melting point of PEO in the networks is higher and increases with the increase of PEO in the interpenetrate networks. Wide-angle X-ray diffraction results show that the PEO crystallite size perpendicular to the (120) plane is not affected as much as PEO in silica networks. (C) 2001 Elsevier Science Ltd. All rights reserved.
Resumo:
Interpenetrating polymer networks (IPNs) based on polyacrylate (poly(polyethylene glycol diacrylate), PEGDA) and epoxy(diglycidyl ether of bisphenol A, DGEBA) were prepared simultaneously Dynamic mechanical properties of the SINs (simultaneous interpenetrating networks) with various compositions were studied. Enhanced mechanical properties were found in this case. From the point of view of pre-swollen networks, all of the PEGDA/DGEBA IPNs were composed of the individual pre-swollen networks. A micro-phase segregation system was produced in the SIN. Glass transition temperatures shifted inward, which was attributed to molecular packing effects or mutual-entanglements of molecular segments among the individual pre-swollen networks. In accordance with the additivity of properties, namely the parallel model, the entanglement density between the two polymer networks reached its maximum at 50/50 PEGDA/DGEBA IPN.
Resumo:
The synthesis and properties of simultaneously interpenetrating networks (SINs) based on poly(polyethylene glycol diacrylate) (PEGDA) and epoxy (diglycidyl ether of bisphenol A, DGEBA) were studied. The effect of compositional variation on the morphology and properties of products was investigated. The swelling coefficient, densities, glass transition behavior, and thermal stability of these interpenetrating networks (IPNs) are discussed. Microphase separation morphological structures were found in all PEGDA/DGEBA IPNs. Decreased swelling ratios compared to the calculated swelling coefficients based on the weight additivity of the components were obtained after the formation of IPNs. Increased density and thermal stability were also obtained in these IPNs, implying the existence of interpenetration (topological entanglements) among the component networks.
Resumo:
Interpenetrating polymer networks of polyepichlorohydrin-based polyurethane/poly(MMA-co-St) have been prepared with simultaneous mettled by changing the weight fraction of MMA(W-MMA) in copolymer of MMA with styrene. The IPNs have been studied by DSC, TEM and dynamic mechanical spectroscopy(DMS). The results show that the IPNs have only one T-g, when W-MMA is greater than 0. 6. But when W-MMA IMA is less than 0. 4, the IPNs have two T(g)s, and phase separation is observed on TEM. The phenomenon is explained according to the solubility parameters(delta) and the fraction of hydrogen bond(delta(h)) of P (MMA-co-St). The study reveals that there is a close correlation among the delta, domain size and mechanical properties of PU (PECH)/P(MMA-co-St) IPN.
Resumo:
We report here the nonlinear rheological properties of metallo-supramolecular networks formed by the reversible cross-linking of semi-dilute unentangled solutions of poly(4-vinylpyridine) (PVP) in dimethyl sulfoxide (DMSO). The reversible cross-linkers are bis-Pd(II) or bis-Pt(II) complexes that coordinate to the pyridine functional groups on the PVP. Under steady shear, shear thickening is observed above a critical shear rate, and that critical shear rate is experimentally correlated with the lifetime of the metal-ligand bond. The onset and magnitude of the shear thickening depend on the amount of cross-linkers added. In contrast to the behavior observed in most transient networks, the time scale of network relaxation is found to increase during shear thickening. The primary mechanism of shear thickening is ascribed to the shear-induced transformation of intrachain cross-linking to interchain cross-linking, rather than nonlinear high tension along polymer chains that are stretched beyond the Gaussian range.
Resumo:
he influence of poly(ethylene glycol) (PEG) plasticiser content and molecular weight on the physicochemical properties of films cast from aqueous blends of poly(methyl vinyl ether-co-maleic acid) was investigated using thermal analysis, swelling studies, scanning electron microscopy (SEM) and attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy. FTIR spectroscopy revealed a shift of the CO peak from 1708 to 1731 cm-1, indicating that an esterification reaction had occurred upon heating, thus producing crosslinked films. Higher molecular weight PEGs (10,000 and 1000 Da, respectively), having greater chain length, producing hydrogel networks with lower crosslink densities and higher average molecular weight between two consecutive crosslinks. Accordingly, such materials exhibited higher swelling rates. Hydrogels crosslinked with a low molecular weight PEG (PEG 200) showed rigid networks with high crosslink densities and, therefore, lower swelling rates. Polymer:plasticizer ratio alteration did not yield any discernable patterns, regardless of the method of analysis. The polymer–water interaction parameter (?) increased with increases in the crosslink density. SEM studies showed that porosity of the crosslinked films increased with increasing PEG MW, confirming what had been observed with swelling studies and thermal analysis, that the crosslink density must be decreased as the Mw of the crosslinker is increased. Hydrogels containing PMVE/MA/PEG 10,000 could be used for rapid delivery of drug, due to their low crosslink density. Moderately crosslinked PMVE/MA/PEG 1000 hydrogels or highly crosslinked PMVE/MA/PEG 200 systems could then be used in controlling the drug delivery rates. We are currently evaluating these systems, both alone and in combination, for use in sustained release drug delivery devices.
Resumo:
Thermoresponsive polymeric platforms are used to optimise drug delivery in pharmaceutical systems and bioactive medical devices. However, the practical application of these systems is compromised by their poor mechanical properties. This study describes the design of thermoresponsive semi-interpenetrating polymer networks (s-IPNs) based on cross-linked p(NIPAA) or p(NIPAA-co-HEMA) hydrogels containing poly(e-caprolactone) designed to address this issue. Using DSC, the lower critical solution temperature of the co-polymer and p(NIPAA) matrices were circa 34 °C and 32 °C, respectively. PCL was physically dispersed within the hydrogel matrices as confirmed using confocal scanning laser microscopy and DSC and resulted in marked changes in the mechanical properties (ultimate tensile strength, Young's modulus) without adversely compromising the elongation properties. P(NIPAA) networks containing dispersed PCL exhibited thermoresponsive swelling properties following immersion in buffer (pH 7), with the equilibrium-swelling ratio being greater at 20 °C than 37 °C and greatest for p(NIPAA)/PCL systems at 20 °C. The incorporation of PCL significantly lowered the equilibrium swelling ratio of the various networks but this was not deemed practically significant for s-IPNs based on p(NIPAA). Thermoresponsive release of metronidazole was observed from s-IPN composed of p(NIPAA)/PCL at 37 °C but not from p(NIPAA-co-HEMA)/PCL at this temperature. In all other platforms, drug release at 20 °C was significantly similar to that at 37 °C and was diffusion controlled. This study has uniquely described a strategy by which thermoresponsive drug release may be performed from polymeric platforms with highly elastic properties. It is proposed that these materials may be used clinically as bioactive endotracheal tubes, designed to offer enhanced resistance to ventilator associated pneumonia, a clinical condition associated with the use of endotracheal tubes where stimulus responsive drug release from biomaterials of significant mechanical properties would be advantageous. © 2012 Elsevier B.V. All rights reserved.
Resumo:
The influence of poly(ethylene glycol) (PEG) plasticiser content and molecular weight on the physicochemical properties of films cast from aqueous blends of poly(methyl vinyl ether-co-maleic acid) was investigated using thermal analysis, swelling studies, scanning electron microscopy (SEM) and attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy. FTIR spectroscopy revealed a shift of the C{double bond, long}O peak from 1708 to 1731 cm, indicating that an esterification reaction had occurred upon heating, thus producing crosslinked films. Higher molecular weight PEGs (10,000 and 1000 Da, respectively), having greater chain length, producing hydrogel networks with lower crosslink densities and higher average molecular weight between two consecutive crosslinks. Accordingly, such materials exhibited higher swelling rates. Hydrogels crosslinked with a low molecular weight PEG (PEG 200) showed rigid networks with high crosslink densities and, therefore, lower swelling rates. Polymer:plasticizer ratio alteration did not yield any discernable patterns, regardless of the method of analysis. The polymer-water interaction parameter (?) increased with increases in the crosslink density. SEM studies showed that porosity of the crosslinked films increased with increasing PEG MW, confirming what had been observed with swelling studies and thermal analysis, that the crosslink density must be decreased as the M of the crosslinker is increased. Hydrogels containing PMVE/MA/PEG 10,000 could be used for rapid delivery of drug, due to their low crosslink density. Moderately crosslinked PMVE/MA/PEG 1000 hydrogels or highly crosslinked PMVE/MA/PEG 200 systems could then be used in controlling the drug delivery rates. We are currently evaluating these systems, both alone and in combination, for use in sustained release drug delivery devices. © 2008 Elsevier Ltd. All rights reserved.
Resumo:
The efficacious delivery of antigens to antigen-presenting cells (APCs), in particular, to dendritic cells (DCs), and their subsequent activation remains a significant challenge in the development of effective vaccines. This study highlights the potential of dissolving microneedle (MN) arrays laden with nanoencapsulated antigen to increase vaccine immunogenicity by targeting antigen specifically to contiguous DC networks within the skin. Following in situ uptake, skin-resident DCs were able to deliver antigen-encapsulated poly-d,l-lactide-co-glycolide (PGLA) nanoparticles to cutaneous draining lymph nodes where they subsequently induced significant expansion of antigen-specific T cells. Moreover, we show that antigen-encapsulated nanoparticle vaccination via microneedles generated robust antigen-specific cellular immune responses in mice. This approach provided complete protection in vivo against both the development of antigen-expressing B16 melanoma tumors and a murine model of para-influenza, through the activation of antigen-specific cytotoxic CD8(+) T cells that resulted in efficient clearance of tumors and virus, respectively. In addition, we show promising findings that nanoencapsulation facilitates antigen retention into skin layers and provides antigen stability in microneedles. Therefore, the use of biodegradable polymeric nanoparticles for selective targeting of antigen to skin DC subsets through dissolvable MNs provides a promising technology for improved vaccination efficacy, compliance, and coverage.
Resumo:
Background Over 20 million people in the US are living with an implantable medical device [ADDIN RW.CITE{{3114 Higgins,DavidM 2009}}1], with similar figures anticipated for Europe. Complications in the use of medical implants include the Foreign Body Response (FBR) characterised by macrophage adherence and fusion, and device-related infection due to bacterial biofilm formationADDIN RW.CITE{{3124 Harding,JacquelineL 2014}}2. Both can have detrimental consequences on the structural and functional integrity of the medical device [ADDIN RW.CITE{{3101 Anderson,JamesM 2008; 3124 Harding,JacquelineL 2014}}2,3], often necessitating removal; a painful and expensive procedure [ADDIN RW.CITE{{3121 Mah,Thien-FahC 2001}}4]. Materials are sought to attenuate both the FBR and device-related infection, leading to medical devices with improved biocompatibility and performance. Objectives The present work involves development of a semi-interpenetrating network (SIPN) hydrogel containing polygalacturonic acid (PGA), a biopolysaccharide similar in structure to hyaluronic acid. We aim to synthesise, characterise and determine the in vitro biocompatibility of the developed SIPN. Results & Discussion We have successfully incorporated PGA into a poly(HEMA) based hydrogel, which shows favourable swelling and wettability. The surface topography appears altered in comparison to the control material, with pronounced micrometer-scale features. In terms of in vitro performance, the SIPN showed increased protein adsorption, and biofilm formation (Staphylococcus epidermidis and Escherichia coli, up to 1 Log CFU/sample greater than control). However the SIPN displayed minimal cytotoxicity towards L929 fibroblasts, and was resistant to the adherence of RAW 264.7 macrophages. Conclusions The PGA incorporated SIPN lacks cytotoxicity and shows reduced macrophage adherence, however the increased biofilm formation highlights a concern regarding possible device related infection in clinical use. Future work will focus on strategies to reduce bacterial adherence, while maintaining biocompatibility.
Resumo:
Motivated by the need for designing efficient and robust fully-distributed computation in highly dynamic networks such as Peer-to-Peer (P2P) networks, we study distributed protocols for constructing and maintaining dynamic network topologies with good expansion properties. Our goal is to maintain a sparse (bounded degree) expander topology despite heavy {\em churn} (i.e., nodes joining and leaving the network continuously over time). We assume that the churn is controlled by an adversary that has complete knowledge and control of what nodes join and leave and at what time and has unlimited computational power, but is oblivious to the random choices made by the algorithm. Our main contribution is a randomized distributed protocol that guarantees with high probability the maintenance of a {\em constant} degree graph with {\em high expansion} even under {\em continuous high adversarial} churn. Our protocol can tolerate a churn rate of up to $O(n/\poly\log(n))$ per round (where $n$ is the stable network size). Our protocol is efficient, lightweight, and scalable, and it incurs only $O(\poly\log(n))$ overhead for topology maintenance: only polylogarithmic (in $n$) bits needs to be processed and sent by each node per round and any node's computation cost per round is also polylogarithmic. The given protocol is a fundamental ingredient that is needed for the design of efficient fully-distributed algorithms for solving fundamental distributed computing problems such as agreement, leader election, search, and storage in highly dynamic P2P networks and enables fast and scalable algorithms for these problems that can tolerate a large amount of churn.
Resumo:
We study the fundamental Byzantine leader election problem in dynamic networks where the topology can change from round to round and nodes can also experience heavy {\em churn} (i.e., nodes can join and leave the network continuously over time). We assume the full information model where the Byzantine nodes have complete knowledge about the entire state of the network at every round (including random choices made by all the nodes), have unbounded computational power and can deviate arbitrarily from the protocol. The churn is controlled by an adversary that has complete knowledge and control over which nodes join and leave and at what times and also may rewire the topology in every round and has unlimited computational power, but is oblivious to the random choices made by the algorithm. Our main contribution is an $O(\log^3 n)$ round algorithm that achieves Byzantine leader election under the presence of up to $O({n}^{1/2 - \epsilon})$ Byzantine nodes (for a small constant $\epsilon > 0$) and a churn of up to \\$O(\sqrt{n}/\poly\log(n))$ nodes per round (where $n$ is the stable network size).The algorithm elects a leader with probability at least $1-n^{-\Omega(1)}$ and guarantees that it is an honest node with probability at least $1-n^{-\Omega(1)}$; assuming the algorithm succeeds, the leader's identity will be known to a $1-o(1)$ fraction of the honest nodes. Our algorithm is fully-distributed, lightweight, and is simple to implement. It is also scalable, as it runs in polylogarithmic (in $n$) time and requires nodes to send and receive messages of only polylogarithmic size per round.To the best of our knowledge, our algorithm is the first scalable solution for Byzantine leader election in a dynamic network with a high rate of churn; our protocol can also be used to solve Byzantine agreement in a straightforward way.We also show how to implement an (almost-everywhere) public coin with constant bias in a dynamic network with Byzantine nodes and provide a mechanism for enabling honest nodes to store information reliably in the network, which might be of independent interest.