Polymer matrix composites research at NASA Lewis Research Center

NASA Technical Reports Server (NTRS)

Serafini, T. T.

1982-01-01

The in situ polymerization of monomer reactants (PMR) approach was demonstrated to be a powerful approach for solving many of the processing difficulties associated with the use of high temperature resistant polymers as matrix resins in high performance composites. The PMR-15 polyimide provides the best overall balance of processing characteristics and elevated temperature properties. The excellent properties and commercial availability of composite materials based on PMR-15 led to their acceptance as viable engineering materials. The PMR-15 composites are used to produce a variety of high quality structural components.

Approaches to polymer-derived CMC matrices

NASA Technical Reports Server (NTRS)

Hurwitz, Frances I.

1992-01-01

The use of polymeric precursors to ceramics permits the fabrication of large, complex-shaped ceramic matrix composites (CMC's) at temperatures which do not degrade the fiber. Processing equipment and techniques readily available in the resin matrix composite industry can be adapted for CMC fabrication using this approach. Criteria which influence the choice of candidate precursor polymers, the use of fillers, and the role of fiber architecture and ply layup are discussed. Three polymer systems, polycarbosilanes, polysilazanes, and polysilsesquioxanes, are compared as candidate ceramic matrix precursors.

Interpenetrating polymer network approach to tougher and more microcracking resistant high temperature polymers. I - LaRC-RP40

NASA Technical Reports Server (NTRS)

Pater, Ruth H.; Morgan, Cassandra D.

1988-01-01

Interpenetrating polymer networks in the form of the LaRC-RP40 resin, prepared by the in situ polymerization of a thermosetting imide prepolymer and thermoplastic monomer reactants, are presently used to obtain toughness and microcracking resistance in a high-temperature polymer. Attention is presently given to the processing, physical, and mechanical properties, as well as the thermooxidative stability, of both the neat resin and the resin as a graphite fiber-reinforced matrix. Microcracking after thermal cycling was also tested. LaRC-RP40 exhibits significant resin fracture toughness improvements over the PMR-15 high-temperature matrix resin.

Interpenetrating polymer network approach to tougher and more microcracking resistant high temperature polymers. I. LaRC-RP40

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pater, R.H.; Morgan, C.D.

1988-10-01

Interpenetrating polymer networks in the form of the LaRC-RP40 resin, prepared by the in situ polymerization of a thermosetting imide prepolymer and thermoplastic monomer reactants, are presently used to obtain toughness and microcracking resistance in a high-temperature polymer. Attention is presently given to the processing, physical, and mechanical properties, as well as the thermooxidative stability, of both the neat resin and the resin as a graphite fiber-reinforced matrix. Microcracking after thermal cycling was also tested. LaRC-RP40 exhibits significant resin fracture toughness improvements over the PMR-15 high-temperature matrix resin. 16 references.

Thermal/Mechanical Durability of Polymer-Matrix Composites in Cryogenic Environments

NASA Technical Reports Server (NTRS)

Gates, Thomas S.; Whitley, Karen S.; Grenoble, Ray W.; Bandorawalla, Tozer

2003-01-01

In order to increase the reliability of the next generation of space transportation systems, the mechanical behavior of polymeric-matrix composite (PMC) materials at cryogenic temperatures must be investigated. This paper presents experimental data on the residual mechanical properties of a carbon fiber polymeric composite, IM7/PETI-5 as a function of temperature and aging. Tension modulus and strength were measured at room temperature, -196 C, and -269 C on five different specimens ply lay-ups. Specimens were preconditioned with one set of coupons being isothermally aged for 576 hours at -184 C, in an unloaded state. Another set of corresponding coupons were mounted in constant strain fixtures such that a constant uniaxial strain was applied to the specimens for 576 hours at -184 C. A third set was mechanically cycled in tension at -184 C. The measured properties indicated that temperature, aging, and loading mode can all have significant influence on performance. Moreover, this influence is a strong function of laminate stacking sequence. Thermal-stress calculations based on lamination theory predicted that the transverse tensile ply stresses could be quite high for cryogenic test temperatures. Microscopic examination of the surface morphology showed evidence of degradation along the exposed edges of the material because of aging at cryogenic temperatures. ________________

Activation energy associated with the electromigration of oligosaccharides through viscosity modifier and polymeric additive containing background electrolytes.

PubMed

Kerékgyártó, Márta; Járvás, Gábor; Novák, Levente; Guttman, András

2016-02-01

The activation energy related to the electromigration of oligosaccharides can be determined from their measured electrophoretic mobilities at different temperatures. The effects of a viscosity modifier (ethylene glycol) and a polymeric additive (linear polyacrylamide) on the electrophoretic mobility of linear sugar oligomers with α1-4 linked glucose units (maltooligosaccharides) were studied in CE using the activation energy concept. The electrophoretic separations of 8-aminopyrene-1,3,6-trisulfonate-labeled maltooligosaccharides were monitored by LIF detection in the temperature range of 20-50°C, using either 0-60% ethylene glycol (viscosity modifier) or 0-3% linear polyacrylamide (polymeric additive) containing BGEs. Activation energy curves were constructed based on the slopes of the Arrhenius plots. With the use of linear polyacrylamide additive, solute size-dependent activation energy variations were found for the maltooligosaccharides with polymerization degrees below and above maltoheptaose (DP 7), probably due to molecular conformation changes and possible matrix interaction effects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Initiator and Photocatalyst-Free Visible Light Induced One-Pot Reaction: Concurrent RAFT Polymerization and CuAAC Click Reaction.

PubMed

Wang, Jie; Wang, Xinbo; Xue, Wentao; Chen, Gaojian; Zhang, Weidong; Zhu, Xiulin

2016-05-01

A new, visible light-catalyzed, one-pot and one-step reaction is successfully employed to design well-controlled side-chain functionalized polymers, by the combination of ambient temperature revisible addtion-fragmentation chain transfer (RAFT) polymerization and click chemistry. Polymerizations are well controlled in a living way under the irradiation of visible light-emitting diode (LED) light without photocatalyst and initiator, using the trithiocarbonate agent as iniferter (initiator-transfer agent-terminator) agent at ambient temperature. Fourier transfer infrared spectroscopy (FT-IR), NMR, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) data confirm the successful one-pot reaction. Compared to the reported zero-valent metal-catalyzed one-pot reaction, the polymerization rate is much faster than that of the click reaction, and the visible light-catalyzed one-pot reaction can be freely and easily regulated by turning on and off the light. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[In Situ Polymerization and Characterization of Hydroxyapatite/polyurethane Implanted Material].

PubMed

Gu, Muqing; Xiao, Fengjuan; Liang, Ye; Yue, Lin; Li, Song; Li, Lanlan; Feng, Feifei

2015-08-01

In order to improve the interfacial bonding strength of hydroxyapatite/polyurethane implanted material and dispersion of hydroxyapatite in the polyurethane matrix, we in the present study synthesized nano-hydroxyapatite/polyurethane composites by in situ polymerization. We then characterized and analyzed the fracture morphology, thermal stability, glass transition temperature and mechanical properties. We seeded MG63 cells on composites to evaluate the cytocompatibility of the composites. In situ polymerization could improve the interfacial bonding strength, ameliorate dispersion of hydroxyapatite in the properties of the composites. After adding 20 wt% hydroxyapatite into the polyurethane, the thermal stability was improved and the glass transition temperatures were increased. The tensile strength and maximum elongation were 6.83 MPa and 861.17%, respectively. Compared with those of pure polyurethane the tensile strength and maximum elongation increased by 236.45% and 143.30%, respectively. The composites were helpful for cell adhesion and proliferation in cultivation.

Effect of surface preparation on the failure load of a highly filled composite bonded to the polymer-monomer matrix of a fiber-reinforced composite.

PubMed

Shimizu, Hiroshi; Tsue, Fumitake; Chen, Zhao-Xun; Takahashi, Yutaka

2009-04-01

The purpose of the present study was to evaluate the effect of surface preparation on the maximum fracture load value of a highly filled composite bonded to the polymer-monomer matrix of a fiber-reinforced composite. A polymer-monomer matrix was made by mixing urethane dimethacrylate and triethyleneglycol dimethacrylate at a ratio of 1:1 with camphorquinone and 2-dimethylaminoethyl methacrylate as a light initiator. The matrix was then polymerized in a disk-shaped silicone mold with a light-polymerizing unit. The flat surfaces of the polymer-monomer matrix disk were prepared in one of the following ways: (1) without preparation; (2) application of silane coupling agent; or (3) application of matrix liquid and prepolymerization. A highly filled composite material was applied and polymerized with a light-polymerizing unit. Additional test specimens made entirely of the polymer-monomer matrix were fabricated as references; the disk and cylinder were fabricated in one piece using a mold specially made for the present study (group 4). Half the specimens were thermocycled up to 10,000 times in water with a 1-minute dwell time at each temperature (5 degrees C and 55 degrees C). The maximum fracture load values were determined using a universal testing machine (n = 10). The maximum fracture loads for group 3 were significantly enhanced both before and after thermocycling, whereas the maximum fracture loads of group 2 were significantly enhanced before thermocycling (p < 0.05); however, the failure loads decreased for all groups after thermocycling (p < 0.05). All the specimens in groups 1 and 2 debonded during thermocycling. The failure load of group 3 was significantly lower than that of group 4 both before and after thermocycling (p < 0.05). Within the limitations of the current in vitro study, the application and prepolymerization of a mixed dimethacrylate resin liquid prior to the application of a highly filled composite was an effective surface preparation for the polymer-monomer matrix of a fiber-reinforced composite; however, the bond durability may be insufficient.

Thermal/Mechanical Response and Damage Growth in Polymeric Composites at Cryogenic Temperatures

NASA Technical Reports Server (NTRS)

Whitley, Karen S.; Gates, Thomas S.

2002-01-01

In order to increase the reliability of the next generation of space transportation systems, the mechanical behavior of polymeric matrix composite (PMC) materials at cryogenic temperatures must be investigated. This paper presents experimental data on the residual mechanical properties of a carbon fiber polymeric composite, IM7/PETI-5 both before and after aging at cryogenic temperatures. Tension modulus and strength were measured at room temperature, -196 C, and -269 C on five different specimen ply lay-ups, [0](sub 12), [90](sub 12), [+/-45](sub 3S), [+/-25](sub 3s) and [45,90(sub 3),-45,0(sub 3),-45,90(sub 3),45]. Specimens were preconditioned with one set of coupons being isothermally aged for 555 hours at -184 C in an unloaded state. Another set of corresponding coupons were mounted in constant displacement fixtures such that a constant uniaxial strain was applied to the specimens for 555 hours at -184 C. The measured lamina level properties indicated that cryogenic temperatures have an appreciable influence on behavior, and residual stress calculations based on lamination theory showed that the transverse tensile ply stresses could be quite high for cryogenic test temperatures. Microscopic examination of the surface morphology showed evidence of degradation along the exposed edges of the material due to aging at cryogenic temperatures.

Frontal Polymerization of Dicyclopentadiene: A Numerical Study.

PubMed

Goli, Elyas; Robertson, Ian D; Geubelle, Philippe H; Moore, Jeffrey S

2018-04-26

As frontal polymerization is being considered as a faster and more energy efficient manufacturing technique for polymer-matrix fiber-reinforced composites, we perform a finite-element-based numerical study of the initiation and propagation of a polymerization front in dicyclopentadiene (DCPD). The transient thermochemical simulations are complemented by an analytical study of the steady-state propagation of the polymerization front, allowing to draw a direct link between the cure kinetics model and the key characteristics of the front, i.e., front velocity and characteristic length scales. The second part of this study focuses on the prediction of the temperature spike associated with the merger of two polymerization fronts. The thermal peak, which might be detrimental to the properties of the polymerized material, is due to the inability of the heat associated with the highly exothermic reaction to be dissipated when the two fronts merge. The analysis investigates how the amplitude of the thermal spike is affected by the degree of cure at the time of the front merger.

Fibronectin Deposition Participates in Extracellular Matrix Assembly and Vascular Morphogenesis

PubMed Central

Hielscher, Abigail; Ellis, Kim; Qiu, Connie; Porterfield, Josh; Gerecht, Sharon

2016-01-01

The extracellular matrix (ECM) has been demonstrated to facilitate angiogenesis. In particular, fibronectin has been documented to activate endothelial cells, resulting in their transition from a quiescent state to an active state in which the cells exhibit enhanced migration and proliferation. The goal of this study is to examine the role of polymerized fibronectin during vascular tubulogenesis using a 3 dimensional (3D) cell-derived de-cellularized matrix. A fibronectin-rich 3D de-cellularized ECM was used as a scaffold to study vascular morphogenesis of endothelial cells (ECs). Confocal analyses of several matrix proteins reveal high intra- and extra-cellular deposition of fibronectin in formed vascular structures. Using a small peptide inhibitor of fibronectin polymerization, we demonstrate that inhibition of fibronectin fibrillogenesis in ECs cultured atop de-cellularized ECM resulted in decreased vascular morphogenesis. Further, immunofluorescence and ultrastructural analyses reveal decreased expression of stromal matrix proteins in the absence of polymerized fibronectin with high co-localization of matrix proteins found in association with polymerized fibronectin. Evaluating vascular kinetics, live cell imaging showed that migration, migration velocity, and mean square displacement, are disrupted in structures grown in the absence of polymerized fibronectin. Additionally, vascular organization failed to occur in the absence of a polymerized fibronectin matrix. Consistent with these observations, we tested vascular morphogenesis following the disruption of EC adhesion to polymerized fibronectin, demonstrating that block of integrins α5β1 and αvβ3, abrogated vascular morphogenesis. Overall, fibronectin deposition in a 3D cell-derived de-cellularized ECM appears to be imperative for matrix assembly and vascular morphogenesis. PMID:26811931

Polymeric phase change nanocomposite (PMMA/Fe:ZnO) for electronic packaging application

NASA Astrophysics Data System (ADS)

Maji, Pranabi; Choudhary, Ram Bilash; Majhi, Malati

2018-01-01

This paper reported the effect of Fe-doped ZnO (Fe:ZnO) nanoparticles on the structural, morphological, thermal, optical and dielectric properties of PMMA matrix. Fe-doped ZnO nanoparticle was synthesized by co-precipitation method, after its surface modification incorporated into the PMMA matrix by free radical polymerization method. The phase analysis and crystal structure were investigated by XRD and FTIR technique. These studies confirmed the chemical structure of the PMMA/Fe:ZnO nanocomposite. FESEM image showed the pyramidal shape and high porosity of PMMA/Fe:ZnO nanocomposite. Thermal analysis of the sample was carried out by thermo-gravimetric analyzer. PMMA/Fe:ZnO nanocomposite was found to have better thermal stability compared to pure one. Broadband dielectric spectroscopic technique was used to investigate the transition of electrical properties of Fe-doped ZnO nanoparticle reinforced PMMA matrix in temperature range 313-373 K. The results elucidated a phase transition from glassy to rubbery state at 344 K.

Achieving Continuous Anion Transport Domains Using Block Copolymers Containing Phosphonium Cations

DOE PAGES

Zhang, Wenxu; Liu, Ye; Jackson, Aaron C.; ...

2016-06-22

Triblock and diblock copolymers based on isoprene (Ip) and chloromethylstyrene (CMS) were synthesized in this paper by sequential polymerization using reversible addition–fragmentation chain transfer radical polymerization (RAFT). The block copolymers were quaternized with tris(2,4,6-trimethoxyphenyl)phosphine (Ar 3P) to prepare soluble ionomers. The ionomers were cast from chloroform to form anion exchange membranes (AEMs) with highly ordered morphologies. At low volume fractions of ionic blocks, the ionomers formed lamellar morphologies, while at moderate volume fractions (≥30% for triblock and ≥22% for diblock copolymers) hexagonal phases with an ionic matrix were observed. Ion conductivities were higher through the hexagonal phase matrix than inmore » the lamellar phases. Finally, promising chloride conductivities (20 mS/cm) were achieved at elevated temperatures and humidified conditions.« less

Novel, inorganic composites using porous, alkali-activated, aluminosilicate binders

NASA Astrophysics Data System (ADS)

Musil, Sean

Geopolymers are an inorganic polymeric material composed of alumina, silica, and alkali metal oxides. Geopolymers are chemical and fire resistant, can be used as refractory adhesives, and are processed at or near ambient temperature. These properties make geopolymer an attractive choice as a matrix material for elevated temperature composites. This body of research investigated numerous different reinforcement possibilities and variants of geopolymer matrix material and characterized their mechanical performance in tension, flexure and flexural creep. Reinforcements can then be chosen based on the resulting properties to tailor the geopolymer matrix composites to a specific application condition. Geopolymer matrix composites combine the ease of processing of polymer matrix composites with the high temperature capability of ceramic matrix composites. This study incorporated particulate, unidirectional fiber and woven fiber reinforcements. Sodium, potassium, and cesium based geopolymer matrices were evaluated with cesium based geopolymer showing great promise as a high temperature matrix material. It showed the best strength retention at elevated temperature, as well as a very low coefficient of thermal expansion when crystallized into pollucite. These qualities made cesium geopolymer the best choice for creep resistant applications. Cesium geopolymer binders were combined with unidirectional continuous polycrystalline mullite fibers (Nextel(TM) 720) and single crystal mullite fibers, then the matrix was crystallized to form cubic pollucite. Single crystal mullite fibers were obtained by the internal crystallization method and show excellent creep resistance up to 1400°C. High temperature flexural strength and flexural creep resistance of pollucite and polycrystalline/single-crystal fibers was evaluated at 1000-1400°C.

Thermoset molecular composites

DOEpatents

Benicewicz, Brian C.; Douglas, Elliot P.; Hjelm, Jr., Rex P.

1996-01-01

A polymeric composition including a liquid crystalline polymer and a thermosettable liquid crystalline monomer matrix, said polymeric composition characterized by a phase separation on the scale of less than about 500 Angstroms and a polymeric composition including a liquid crystalline polymer and a liquid crystalline thermoset matrix, said polymeric composition characterized by a phase separation on the scale of less than about 500 Angstroms are disclosed.

Pentacene-based organic thin film transistors, integrated circuits, and active matrix displays on polymeric substrates

NASA Astrophysics Data System (ADS)

Sheraw, Christopher Duncan

2003-10-01

Organic thin film transistors are attractive candidates for a variety of low cost, large area commercial electronics including smart cards, RF identification tags, and flat panel displays. Of particular interest are high performance organic thin film transistors (TFTs) that can be fabricated on flexible polymeric substrates allowing low-cost, lightweight, rugged electronics such as flexible active matrix displays. This thesis reports pentacene organic thin film transistors fabricated on flexible polymeric substrates with record performance, the fastest photolithographically patterned organic TFT integrated circuits on polymeric substrates reported to date, and the fabrication of the organic TFT backplanes used to build the first organic TFT-driven active matrix liquid crystal display (AMLCD), also the first AMLCD on a flexible substrate, ever reported. In addition, the first investigation of functionalized pentacene derivatives used as the active layer in organic thin film transistors is reported. A low temperature (<110°C) process technology was developed allowing the fabrication of high performance organic TFTs, integrated circuits, and large TFT arrays on flexible polymeric substrates. This process includes the development of a novel water-based photolithographic active layer patterning process using polyvinyl alcohol that allows the patterning of organic semiconductor materials for elimination of active layer leakage current without causing device degradation. The small molecule aromatic hydrocarbon pentacene was used as the active layer material to fabricate organic TFTs on the polymeric material polyethylene naphthalate with field-effect mobility as large as 2.1 cm2/V-s and on/off current ratio of 108. These are the best values reported for organic TFTs on polymeric substrates and comparable to organic TFTs on rigid substrates. Analog and digital integrated circuits were also fabricated on polymeric substrates using pentacene TFTs with propagation delay as low as 38 musec and clocked digital circuits that operated at 1.1 kHz. These are the fastest photolithographically patterned organic TFT circuits on polymeric substrates reported to date. Finally, 16 x 16 pentacene TFT pixel arrays were fabricated on polymeric substrates and integrated with polymer dispersed liquid crystal to build an AMLCD. The pixel arrays showed good optical response to changing data signals when standard quarter-VGA display waveforms were applied. This result marks the first organic TFT-driven active matrix liquid crystal display ever reported as well as the first active matrix liquid crystal display on a flexible polymeric substrate. Lastly, functionalized pentacene derivatives were used as the active layer in organic thin film transistor materials. Functional groups were added to the pentacene molecule to influence the molecular ordering so that the amount of pi-orbital overlap would be increased allowing the potential for improved field-effect mobility. The functionalization of these materials also improves solubility allowing for the possibility of solution-processed devices and increased oxidative stability. Organic thin film transistors were fabricated using five different functionalized pentacene active layers. Devices based on the pentacene derivative triisopropylsilyl pentacene were found to have the best performance with field-effect mobility as large as 0.4 cm 2/V-s.

Polymer-phyllosilicate nanocomposites and their preparation

DOEpatents

Chaiko, David J.

2007-01-09

Polymer-phyllosilicate nanocomposites that exhibit superior properties compared to the polymer alone, and methods-for producing these polymer-phyllosilicate nanocomposites, are provided. Polymeric surfactant compatabilizers are adsorbed onto the surface of hydrophilic or natural phyllosilicates to facilitate the dispersal and exfoliation of the phyllosilicate in a polymer matrix. Utilizing polymeric glycol based surfactants, polymeric dicarboxylic acids, polymeric diammonium surfactants, and polymeric diamine surfactants as compatabilizers facilitates natural phyllosilicate and hydrophilic organoclay dispersal in a polymer matrix to produce nanocomposites.

Ladder polymers for use as high temperature stable resins or coatings

NASA Technical Reports Server (NTRS)

Meador, Mary Ann (Inventor)

1990-01-01

An object of the invention is to synthesize a new class of ladder and partial ladder polymers. In accordance with the invention, the new class of ladder and partial ladder polymers are synthesized by polymerizing a bis-dienophile with a bis-diene. Another object of the invention is to provide a fabricated, electrically conducting, void free composite comprising the new class of the ladder and partial ladder polymers described above. The novelty of the invention relates to a new class of ladder and partial ladder polymers and a process for synthesizing these polymers. These polymers are soluble in common organic solvents and are characterized with a unique dehydration property at temperatures of 300 to 400 C to provide thermo-oxidatively stable pentiptycene units along the polymeric backbone. These polymers are further characterized with high softening points and good thermo-oxidative stability properties. Thus these polymers have potential as processable, matrix resins for high temperature composite applications.

On the Injection Molding Processing Parameters of HDPE-TiO2 Nanocomposites

PubMed Central

Mourad, Abdel-Hamid I.; Mozumder, Mohammad Sayem; Mairpady, Anusha; Pervez, Hifsa; Kannuri, Uma Maheshwara

2017-01-01

In recent years, the development and use of polymeric nanocomposites in creating advanced materials has expanded exponentially. A substantial amount of research has been done in order to design polymeric nanocomposites in a safe and efficient manner. In the present study, the impact of processing parameters, such as, barrel temperature, and residence time on the mechanical and thermal properties of high density polyethylene (HDPE)-TiO2 nanocomposites were investigated. Additionally, scanning electron microscopy and X-ray diffraction spectroscopy were used to analyze the dispersion, location, and phase morphology of TiO2 on the HDPE matrix. Mechanical tests revealed that tensile strength of the fabricated HDPE-TiO2 nanocomposites ranged between 22.53 and 26.30 MPa, while the Young’s modulus showed a consistent increase as the barrel temperature increased from 150 °C to 300 °C. Moreover, the thermal stability decreased as the barrel temperature increased. PMID:28772444

On the Injection Molding Processing Parameters of HDPE-TiO₂ Nanocomposites.

PubMed

Mourad, Abdel-Hamid I; Mozumder, Mohammad Sayem; Mairpady, Anusha; Pervez, Hifsa; Kannuri, Uma Maheshwara

2017-01-20

In recent years, the development and use of polymeric nanocomposites in creating advanced materials has expanded exponentially. A substantial amount of research has been done in order to design polymeric nanocomposites in a safe and efficient manner. In the present study, the impact of processing parameters, such as, barrel temperature, and residence time on the mechanical and thermal properties of high density polyethylene (HDPE)-TiO₂ nanocomposites were investigated. Additionally, scanning electron microscopy and X-ray diffraction spectroscopy were used to analyze the dispersion, location, and phase morphology of TiO₂ on the HDPE matrix. Mechanical tests revealed that tensile strength of the fabricated HDPE-TiO₂ nanocomposites ranged between 22.53 and 26.30 MPa, while the Young's modulus showed a consistent increase as the barrel temperature increased from 150 °C to 300 °C. Moreover, the thermal stability decreased as the barrel temperature increased.

Facile and Reliable in Situ Polymerization of Poly(Ethyl Cyanoacrylate)-Based Polymer Electrolytes toward Flexible Lithium Batteries.

PubMed

Cui, Yanyan; Chai, Jingchao; Du, Huiping; Duan, Yulong; Xie, Guangwen; Liu, Zhihong; Cui, Guanglei

2017-03-15

Polycyanoacrylate is a very promising matrix for polymer electrolyte, which possesses advantages of strong binding and high electrochemical stability owing to the functional nitrile groups. Herein, a facile and reliable in situ polymerization strategy of poly(ethyl cyanoacrylate) (PECA) based gel polymer electrolytes (GPE) via a high efficient anionic polymerization was introduced consisting of PECA and 4 M LiClO 4 in carbonate solvents. The in situ polymerized PECA gel polymer electrolyte achieved an excellent ionic conductivity (2.7 × 10 -3 S cm -1 ) at room temperature, and exhibited a considerable electrochemical stability window up to 4.8 V vs Li/Li + . The LiFePO 4 /PECA-GPE/Li and LiNi 1.5 Mn 0.5 O 4 /PECA-GPE/Li batteries using this in-situ-polymerized GPE delivered stable charge/discharge profiles, considerable rate capability, and excellent cycling performance. These results demonstrated this reliable in situ polymerization process is a very promising strategy to prepare high performance polymer electrolytes for flexible thin-film batteries, micropower lithium batteries, and deformable lithium batteries for special purpose.

Self-assembly and reactive molding techniques for controlling the interface and dispersion of the particulate phase in nanocomposites

NASA Astrophysics Data System (ADS)

Pranger, Lawrence A.

This research explored the processing and properties of PNCs using a polyfurfural alcohol (PFA) matrix. The precursor for PFA, furfuryl alcohol (FA) is sourced from feedstocks rich in hemicellulose, such as corn cobs, oat hulls and wood. To exploit FA as a polymerizable solvent, cellulose whiskers (CW) and montmorillonite clay (MMT) were used as the nanoparticle phase. Results from PNC processing show that CW and MMT can be dispersed in the PFA matrix by means of insitu polymerization, without the use of surfactants or dilution in solvents. Both CW and MMT nanoparticles catalyze the polymerization of furfuryl alcohol (FA). Moreover, the insitu intercalative polymerization of FA in the interlayer galleries of MMT leads to the complete exfoliation of the MMT in the PFA matrix. CW and MMT both function as effective matrix modifiers, increasing the thermal stability of PFA nanocomposites compared to pure PFA polymer. The increased thermal stability is seen as significant increases in the onset of degradation and in residual weight at high temperature. This research also explored the surface functionalization of Cu, Ni and Pt substrates by self-assembly of a range of difunctional linker molecules. Characterization by XPS and PM-IRRAS indicate that diisocyanides and dicarboxylic acids both form chemically "sticky" surfaces after self-assembly on Cu and Ni. Sticky surfaces may provide a means of increasing nanoparticle dispersion in metal nanocluster filled PNCs, by increasing their interaction with the matrix polymer. Another potential application for sticky surfaces on Cu is in the ongoing miniaturization of circuit boards. The functionalization of Cu bond pad substrates with linker molecules may provide an alternate means of bonding components to their bond pads, with higher placement accuracy compared to solder bumps.

Fibronectin Matrix Polymerization Regulates Smooth Muscle Cell Phenotype through a Rac1 Dependent Mechanism

PubMed Central

Shi, Feng; Long, Xiaochun; Hendershot, Allison; Miano, Joseph M.; Sottile, Jane

2014-01-01

Smooth muscle cells are maintained in a differentiated state in the vessel wall, but can be modulated to a synthetic phenotype following injury. Smooth muscle phenotypic modulation is thought to play an important role in the pathology of vascular occlusive diseases. Phenotypically modulated smooth muscle cells exhibit increased proliferative and migratory properties that accompany the downregulation of smooth muscle cell marker proteins. Extracellular matrix proteins, including fibronectin, can regulate the smooth muscle phenotype when used as adhesive substrates. However, cells produce and organize a 3-dimensional fibrillar extracellular matrix, which can affect cell behavior in distinct ways from the protomeric 2-dimensional matrix proteins that are used as adhesive substrates. We previously showed that the deposition/polymerization of fibronectin into the extracellular matrix can regulate the deposition and organization of other extracellular matrix molecules in vitro. Further, our published data show that the presence of a fibronectin polymerization inhibitor results in increased expression of smooth muscle cell differentiation proteins and inhibits vascular remodeling in vivo. In this manuscript, we used an in vitro cell culture system to determine the mechanism by which fibronectin polymerization affects smooth muscle phenotypic modulation. Our data show that fibronectin polymerization decreases the mRNA levels of multiple smooth muscle differentiation genes, and downregulates the levels of smooth muscle α-actin and calponin proteins by a Rac1-dependent mechanism. The expression of smooth muscle genes is transcriptionally regulated by fibronectin polymerization, as evidenced by the increased activity of luciferase reporter constructs in the presence of a fibronectin polymerization inhibitor. Fibronectin polymerization also promotes smooth muscle cell growth, and decreases the levels of actin stress fibers. These data define a Rac1-dependent pathway wherein fibronectin polymerization promotes the SMC synthetic phenotype by modulating the expression of smooth muscle cell differentiation proteins. PMID:24752318

Development of a poly(dimethylacrylamide) based matrix material for solid phase high density peptide array synthesis employing a laser based material transfer

NASA Astrophysics Data System (ADS)

Ridder, Barbara; Foertsch, Tobias C.; Welle, Alexander; Mattes, Daniela S.; von Bojnicic-Kninski, Clemens M.; Loeffler, Felix F.; Nesterov-Mueller, Alexander; Meier, Michael A. R.; Breitling, Frank

2016-12-01

Poly(dimethylacrylamide) (PDMA) based matrix materials were developed for laser-based in situ solid phase peptide synthesis to produce high density arrays. In this specific array synthesis approach, amino acid derivatives are embedded into a matrix material, serving as a ;solid; solvent material at room temperature. Then, a laser pulse transfers this mixture to the target position on a synthesis slide, where the peptide array is synthesized. Upon heating above the glass transition temperature of the matrix material, it softens, allowing diffusion of the amino acid derivatives to the synthesis surface and serving as a solvent for peptide bond formation. Here, we synthesized PDMA six-arm star polymers, offering the desired matrix material properties, using atom transfer radical polymerization. With the synthesized polymers as matrix material, we structured and synthesized arrays with combinatorial laser transfer. With densities of up to 20,000 peptide spots per cm2, the resolution could be increased compared to the commercially available standard matrix material. Time-of-Flight Secondary Ion Mass Spectrometry experiments revealed the penetration behavior of an amino acid derivative into the prepared acceptor synthesis surface and the effectiveness of the washing protocols.

Transparent conductive nano-composites

DOEpatents

Geohegan, David Bruce; Ivanov, Ilia N; Puretzky, Alexander A; Jesse, Stephen; Hu, Bin; Garrett, Matthew; Zhao, Bin

2013-09-24

The present invention, in one embodiment, provides a method of forming an organic electric device that includes providing a plurality of carbon nanostructures; and dispersing the plurality of carbon nanostructures in a polymeric matrix to provide a polymeric composite, wherein when the plurality of carbon nanostructures are present at a first concentration an interface of the plurality of carbon nanostructures and the polymeric matrix is characterized by charge transport when an external energy is applied, and when the plurality of carbon nanostructures are present at a second concentration the interface of the plurality of carbon nanostructures and the polymeric matrix are characterized by exciton dissociation when an external energy is applied, wherein the first concentration is less than the second concentration.

Transparent conductive nano-composites

DOEpatents

Geohegan, David Bruce [Knoxville, TN; Ivanov, Ilia N [Knoxville, TN; Puretzky, Alexander A [Knoxville, TN; Jesse, Stephen [Knoxville, TN; Hu, Bin [Knoxville, TN; Garrett, Matthew [Knoxville, TN; Zhao, Bin [Easley, SC

2011-04-12

The present invention, in one embodiment, provides a method of forming an organic electric device that includes providing a plurality of carbon nanostructures; and dispersing the plurality of carbon nanostructures in a polymeric matrix to provide a polymeric composite, wherein when the plurality of carbon nanostructures are present at a first concentration an interface of the plurality of carbon nanostructures and the polymeric matrix is characterized by charge transport when an external energy is applied, and when the plurality of carbon nanostructures are present at a second concentration the interface of the plurality of carbon nanostructures and the polymeric matrix are characterized by exciton dissociation when an external energy is applied, wherein the first concentration is less than the second concentration.

Adhesion strength of norbornene-based self-healing agents to an amine-cured epoxy

NASA Astrophysics Data System (ADS)

Huang, Guang Chun; Lee, Jong Keun; Kessler, Michael R.; Yoon, Sungho

2009-07-01

Self-healing is triggered by crack propagation through embedded microcapsules in an epoxy matrix, which then release the liquid healing agent into the crack plane. Subsequent exposure of the healing agent to the chemical catalyst initiates ring-opening metathesis polymerization (ROMP) and bonding of the crack faces. In order to improve self-healing functionality, it is necessary to enhance adhesion of polymerized healing agent within the crack to the matrix resin. In this study, shear bond strength between different norbornene-based healing agents and an amine-cured epoxy resin was evaluated using the single lap shear test method (ASTM D3163, modified). The healing agents tested include endodicyclopentadiene (endo-DCPD), 5-ethylidene-2-norbornene (ENB) and DCPD/ENB blends. 5-Norbornene-2-methanol (NBM) was used as an adhesion promoter, containing hydroxyl groups to form hydrogen bonds with the amine-cured epoxy. A custom synthesized norbornene-based crosslinking agent was also added to improve adhesion for ENB by increasing the crosslinking density of the adhesive after ROMP. The healing agents were polymerized with varying loadings of the 1st generation Grubbs' catalyst at different reaction times and temperatures.

Stratospheric experiments on curing of composite materials

NASA Astrophysics Data System (ADS)

Chudinov, Viacheslav; Kondyurin, Alexey; Svistkov, Alexander L.; Efremov, Denis; Demin, Anton; Terpugov, Viktor; Rusakov, Sergey

2016-07-01

Future space exploration requires a large light-weight structure for habitats, greenhouses, space bases, space factories and other constructions. A new approach enabling large-size constructions in space relies on the use of the technology of polymerization of fiber-filled composites with a curable polymer matrix applied in the free space environment on Erath orbit. In orbit, the material is exposed to high vacuum, dramatic temperature changes, plasma of free space due to cosmic rays, sun irradiation and atomic oxygen (in low Earth orbit), micrometeorite fluence, electric charging and microgravitation. The development of appropriate polymer matrix composites requires an understanding of the chemical processes of polymer matrix curing under the specific free space conditions to be encountered. The goal of the stratospheric flight experiment is an investigation of the effect of the stratospheric conditions on the uncured polymer matrix of the composite material. The unique combination of low residual pressure, high intensity UV radiation including short-wave UV component, cosmic rays and other aspects associated with solar irradiation strongly influences the chemical processes in polymeric materials. We have done the stratospheric flight experiments with uncured composites (prepreg). A balloon with payload equipped with heater, temperature/pressure/irradiation sensors, microprocessor, carrying the samples of uncured prepreg has been launched to stratosphere of 25-30 km altitude. After the flight, the samples have been tested with FTIR, gel-fraction, tensile test and DMA. The effect of cosmic radiation has been observed. The composite was successfully cured during the stratospheric flight. The study was supported by RFBR grants 12-08-00970 and 14-08-96011.

Polymeric matrix materials for infrared metamaterials

DOEpatents

Dirk, Shawn M; Rasberry, Roger D; Rahimian, Kamyar

2014-04-22

A polymeric matrix material exhibits low loss at optical frequencies and facilitates the fabrication of all-dielectric metamaterials. The low-loss polymeric matrix material can be synthesized by providing an unsaturated polymer, comprising double or triple bonds; partially hydrogenating the unsaturated polymer; depositing a film of the partially hydrogenated polymer and a crosslinker on a substrate; and photopatterning the film by exposing the film to ultraviolet light through a patterning mask, thereby cross-linking at least some of the remaining unsaturated groups of the partially hydrogenated polymer in the exposed portions.

Thermally Stable Siloxane Hybrid Matrix with Low Dielectric Loss for Copper-Clad Laminates for High-Frequency Applications.

PubMed

Kim, Yong Ho; Lim, Young-Woo; Kim, Yun Hyeok; Bae, Byeong-Soo

2016-04-06

We report vinyl-phenyl siloxane hybrid material (VPH) that can be used as a matrix for copper-clad laminates (CCLs) for high-frequency applications. The CCLs, with a VPH matrix fabricated via radical polymerization of resin blend consisting of sol-gel-derived linear vinyl oligosiloxane and bulky siloxane monomer, phenyltris(trimethylsiloxy)silane, achieve low dielectric constant (Dk) and dissipation factor (Df). The CCLs with the VPH matrix exhibit excellent dielectric performance (Dk = 2.75, Df = 0.0015 at 1 GHz) with stability in wide frequency range (1 MHz to 10 GHz) and at high temperature (up to 275 °C). Also, the VPH shows good flame resistance without any additives. These results suggest the potential of the VPH for use in high-speed IC boards.

Structure and physico-mechanical properties of low temperature plasma treated electrospun nanofibrous scaffolds examined with atomic force microscopy.

PubMed

Chlanda, Adrian; Kijeńska, Ewa; Rinoldi, Chiara; Tarnowski, Michał; Wierzchoń, Tadeusz; Swieszkowski, Wojciech

2018-04-01

Electrospun nanofibrous scaffolds are willingly used in tissue engineering applications due to their tunable mechanical, chemical and physical properties. Additionally, their complex openworked architecture is similar to the native extracellular matrix of living tissue. After implantation such scaffolds should provide sufficient mechanical support for cells. Moreover, it is of crucial importance to ensure sterility and hydrophilicity of the scaffold. For this purpose, a low temperature surface plasma treatment can be applied. In this paper, we report physico-mechanical evaluation of stiffness and adhesive properties of electrospun mats after their exposition to low temperature plasma. Complex morphological and mechanical studies performed with an atomic force microscope were followed by scanning electron microscope imaging and a wettability assessment. The results suggest that plasma treatment can be a useful method for the modification of the surface of polymeric scaffolds in a desirable manner. Plasma treatment improves wettability of the polymeric mats without changing their morphology. Copyright © 2018 Elsevier Ltd. All rights reserved.

Monitoring Prepregs As They Cure

NASA Technical Reports Server (NTRS)

Young, P. R.; Gleason, J. R.; Chang, A. C.

1986-01-01

Quality IR spectra obtained in dynamic heating environment. New technique obtains quality infrared spectra on graphite-fiber-reinforced, polymeric-matrix-resin prepregs as they cure. Technique resulted from modification of diffuse reflectance/Fourier transform infrared (DR/FTIR) technique previously used to analyze environmentally exposed cured graphite composites. Technique contribute to better understanding of prepreg chemistry/temperature relationships and development of more efficient processing cycles for advanced materials.

Heat resistant substrates and battery separators made therefrom

NASA Technical Reports Server (NTRS)

Langer, Alois (Inventor); Scala, Luciano C. (Inventor); Ruffing, Charles R. (Inventor)

1976-01-01

A flexible substrate having a caustic resistant support and at least one membrane comprising a solid polymeric matrix containing a network of interconnected pores and interdispersed inorganic filler particles with a ratio of filler: polymer in the polymeric matrix of between about 1:1 to 5:1, is made by coating at least one side of the support with a filler:coating formulation mixture of inorganic filler particles and a caustic resistant, water insoluble polymer dissolved in an organic solvent, and removing the solvent from the mixture to provide a porous network within the polymeric matrix.

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

PubMed Central

Liu, Yayuan; Lin, Dingchang; Liang, Zheng; Zhao, Jie; Yan, Kai; Cui, Yi

2016-01-01

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizing minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm−2 in both carbonate and ether electrolyte. The advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes. PMID:26987481

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

DOE PAGES

Liu, Yayuan; Lin, Dingchang; Liang, Zheng; ...

2016-03-18

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yayuan; Lin, Dingchang; Liang, Zheng

Lithium metal is the ideal anode for the next generation of high-energy-density batteries. Nevertheless, dendrite growth, side reactions and infinite relative volume change have prevented it from practical applications. Here, we demonstrate a promising metallic lithium anode design by infusing molten lithium into a polymeric matrix. The electrospun polyimide employed is stable against highly reactive molten lithium and, via a conformal layer of zinc oxide coating to render the surface lithiophilic, molten lithium can be drawn into the matrix, affording a nano-porous lithium electrode. Importantly, the polymeric backbone enables uniform lithium stripping/plating, which successfully confines lithium within the matrix, realizingmore » minimum volume change and effective dendrite suppression. The porous electrode reduces the effective current density; thus, flat voltage profiles and stable cycling of more than 100 cycles is achieved even at a high current density of 5 mA cm -2 in both carbonate and ether electrolyte. Furthermore, the advantages of the porous, polymeric matrix provide important insights into the design principles of lithium metal anodes.« less

Process for making polymers comprising derivatized carbon nanotubes and compositions thereof

NASA Technical Reports Server (NTRS)

Tour, James M. (Inventor); Bahr, Jeffrey L. (Inventor); Yang, Jiping (Inventor)

2007-01-01

The present invention incorporates new processes for blending derivatized carbon nanotubes into polymer matrices to create new polymer/composite materials. When modified with suitable chemical groups using diazonium chemistry, the nanotubes can be made chemically compatible with a polymer matrix, allowing transfer of the properties of the nanotubes (such as mechanical strength) to the properties of the composite material as a whole. To achieve this, the derivatized (modified) carbon nanotubes are physically blended with the polymeric material, and/or, if desired, allowed to react at ambient or elevated temperature. These methods can be utilized to append functionalities to the nanotubes that will further covalently bond to the host polymer matrix, or directly between two tubes themselves. Furthermore, the nanotubes can be used as a generator of polymer growth, wherein the nanotubes are derivatized with a functional group that is an active part of a polymerization process, which would also result in a composite material in which the carbon nanotubes are chemically involved.

Characterization of silver/polystyrene nanocomposites prepared by in situ bulk radical polymerization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vukoje, Ivana D., E-mail: ivanav@vinca.rs; Vodnik, Vesna V., E-mail: vodves@vinca.rs; Džunuzović, Jasna V., E-mail: jasnav2002@googlemail.com

2014-01-01

Graphical abstract: - Highlights: • Synthesis and characterization of polystyrene nanocomposites based on Ag nanoparticles. • The glass transition temperature decreased in nanocomposites with respect to the pure polymer. • Resistance of the polymer to thermal degradation enhanced with Ag nanoparticles content. - Abstract: Nanocomposites (NCs) with different content of silver nanoparticles (Ag NPs) embeded in polystyrene (PS) matrix were prepared by in situ bulk radical polymerization. The nearly monodisperse Ag NPs protected with oleylamine were synthesized via organic solvo-thermal method and further used as a filler. The as-prepared spherical Ag NPs with diameter of 7.0 ± 1.5 nm weremore » well dispersed in the PS matrix. The structural properties of the resulting Ag/PS NCs were characterized by transmission electron microscope (TEM) and Fourier transform infrared (FTIR) spectroscopy, while optical properties were characterized using optical absorption measurements. The gel permeation chromatography (GPC) measurements showed that the presence of Ag NPs stabilized with oleylamine has no influence on the molecular weight and polydispersity of the PS matrix. The influence of silver content on the thermal properties of Ag/PS NCs was investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results indicated that resistance of PS to thermal degradation was improved upon incorporation of Ag NPs. The Ag/PS NCs have lower glass transition temperatures than neat PS because loosely packed oleylamine molecules at the interface caused the increase of free volume and chain segments mobility near the surface of Ag NPs.« less

Method for encapsulating nanoparticles in a zeolite matrix

DOEpatents

Coker, Eric N.

2007-12-11

A method for preparing a metal nanocluster composite material. A porous zeolitic material is treated with an aqueous metal compound solution to form a metal ion-exchanged zeolitic material, heated at a temperature ramp rate of less than 2.degree. C./min to an elevated temperature, cooled, contacted with an organic monomer and heating to induce polymerization, and heating the composite material to greater than 350.degree. C. under non-oxidizing conditions to form a metal nanocluster-carbon composite material with nanocluster sizes between approximately 0.6 nm and 10 nm.

Chemical approach for controlling nadimide cure temperature and rate

NASA Technical Reports Server (NTRS)

Lauver, R. W. (Inventor)

1985-01-01

Polyimide resins suitable for use as composite matrix materials are formed by copolymerization of maleic and norbornenyl end-capped monomers and oligomers. The copolymers can be cured at temperatures under about 300 C. by controlling the available concentration of the maleic end-capped reactant. This control can be achieved by adding sufficient amounts of said maleic reactant, or by chemical modification of either copolymer, to increase Diels-Alder retrogression of the norbornenyl-capped reactant and/or holding initiation and polymerization to a rate compatible with the availability of the maleic-capped reactant.

Chemical approach for controlling nadimide cure temperature and rate

NASA Technical Reports Server (NTRS)

Lauver, R. W. (Inventor)

1984-01-01

Polyimide resins suitable for use as composite matrix materials are formed by copolymerization of maleic and norbornenyl endcapped monomers and oligomers. The copolymers can be cured at temperatures under about 300 C by controlling the available concentration of the maleic capped reactant. This control can be achieved by adding sufficient amounts of said maleic reactant, or by chemical modification of either copolymer, so as to either increase Diels-Alder retrogression of the norbornenyl capped reactant and/or holding initiation and polymerization to a rate compatible with the availability of the maleic capped reactant.

Chemical approach for controlling nadimide cure temperature and rate

NASA Technical Reports Server (NTRS)

Lauver, R. W. (Inventor)

1985-01-01

Polyimide resins suitable for use as composite matrix materials are formed by copolymerization of maleic and norbornenyl endcapped monomers and oligomers. The copolymers can be cured at temperatures under about 300 C by controlling the available concentration of the maleic endcapped reactant. This control is achieved by adding sufficient amounts of said maleic reactant or by chemical modification of either copolymer, to either increase Diels-Alder retrogression of the norbornenyl capped reactant and/or hold initiation and polymerization to a rate compatible with the availability of the maleic capped reactant.

Structure and component dynamics in binary mixtures of poly(2-(dimethylamino)ethyl methacrylate) with water and tetrahydrofuran: A diffraction, calorimetric, and dielectric spectroscopy study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goracci, G., E-mail: sckgorag@ehu.es; Arbe, A.; Alegría, A.

2016-04-21

We have combined X-ray diffraction, neutron diffraction with polarization analysis, small angle neutron scattering, differential scanning calorimetry, and broad band dielectric spectroscopy to investigate the structure and dynamics of binary mixtures of poly (2-(dimethylamino)ethyl methacrylate) with either water or tetrahydrofuran (THF) at different concentrations. Aqueous mixtures are characterized by a highly heterogeneous structure where water clusters coexist with an underlying nano-segregation of main chains and side groups of the polymeric matrix. THF molecules are homogeneously distributed among the polymeric nano-domains for concentrations of one THF molecule/monomer or lower. A more heterogeneous situation is found for higher THF amounts, but withoutmore » evidences for solvent clusters. In THF-mixtures, we observe a remarkable reduction of the glass-transition temperature which is enhanced with increasing amount of solvent but seems to reach saturation at high THF concentrations. Adding THF markedly reduces the activation energy of the polymer β-relaxation. The presence of THF molecules seemingly hinders a slow component of this process which is active in the dry state. The aqueous mixtures present a strikingly broad glass-transition feature, revealing a highly heterogeneous behavior in agreement with the structural study. Regarding the solvent dynamics, deep in the glassy state all data can be described by an Arrhenius temperature dependence with a rather similar activation energy. However, the values of the characteristic times are about three orders of magnitude smaller for THF than for water. Water dynamics display a crossover toward increasingly higher apparent activation energies in the region of the onset of the glass transition, supporting its interpretation as a consequence of the freezing of the structural relaxation of the surrounding matrix. The absence of such a crossover (at least in the wide dynamic window here accessed) in THF is attributed to the lack of cooperativity effects in the relaxation of these molecules within the polymeric matrix.« less

Matrix dominated stress/strain behavior in polymeric composites: Effects of hold time, nonlinearity and rate dependency

NASA Technical Reports Server (NTRS)

Gates, Thomas S.

1992-01-01

In order to understand matrix dominated behavior in laminated polymer matrix composites, an elastic/viscoplastic constitutive model was developed and used to predict stress strain behavior of off-axis and angle-ply symmetric laminates under in-plane, tensile axial loading. The model was validated for short duration tests at elevated temperatures. Short term stress relaxation and short term creep, strain rate sensitivity, and material nonlinearity were accounted for. The testing times were extended for longer durations, and periods of creep and stress relaxation were used to investigate the ability of the model to account for long term behavior. The model generally underestimated the total change in strain and stress for both long term creep and long term relaxation respectively.

Composite Materials With Uncured Epoxy Matrix Exposed in Stratosphere During NASA Stratospheric Balloon Flight

NASA Technical Reports Server (NTRS)

Kondyurin, Alexey; Kondyurina, Irina; Bilek, Marcela; de Groh, Kim K.

2013-01-01

A cassette of uncured composite materials with epoxy resin matrixes was exposed in the stratosphere (40 km altitude) over three days. Temperature variations of -76 to 32.5C and pressure up to 2.1 torr were recorded during flight. An analysis of the chemical structure of the composites showed, that the polymer matrix exposed in the stratosphere becomes crosslinked, while the ground control materials react by way of polymerization reaction of epoxy groups. The space irradiations are considered to be responsible for crosslinking of the uncured polymers exposed in the stratosphere. The composites were cured on Earth after landing. Analysis of the cured composites showed that the polymer matrix remains active under stratospheric conditions. The results can be used for predicting curing processes of polymer composites in a free space environment during an orbital space flight.

Carbon matrix based magnetic nanocomposites for potential biomedical applications.

PubMed

Izydorzak-Wozniak, M; Leonowicz, M

2014-03-01

It was found that by varying the pyrolysis temperature of the polymeric precursor, carbon matrix magnetic nanocomposites with different constitution and fractions of magnetic component were made. X-ray diffraction, transmission electron microscopy and Raman spectroscopy revealed the presence of nanocrystallites (NCs) of Co, Fe3C and Ni embedded in porous, partially-graphitized carbon matrix. Vibrating sample magnetometer measurements enabled to determine the correlation between NCs size distribution and magnetic properties. The magnetic studies confirmed that the coercivity, saturation and remanent magnetizations, as well as fraction of the magnetic component depend on the pyrolysis temperature. The Co#C and Fe3C#C composites exhibited ferromagnetic behavior with a remanent to saturation magnetization (M(R)/M(S)) ratio ranging from 0.25 to 0.3, whereas in the Ni containing samples a relatively small M(R)/M(S) ratio point to significant contribution of superparamagnetic interactions. As the carbon matrix magnetic nanocomposites are proposed for biomedical application the basic cytotoxicity test were performed to evaluate a potential toxic effect of the materials on MG-63 cells line.

Characterization of Mechanical Damage Mechanisms in Ceramic and Polymeric Matrix Composite Materials

DTIC Science & Technology

1991-11-01

microplasticity is a vital factor in the compressive failure of even these very hard materials under essentially all conditions (temperature, strain rate...OF CONTENTS Pag= The Compressive Strength of Strong Ceramics: Microplasticity Versus 1 Microfracture Abstract 1 1. Introduction 2 2. Hardness 3 3...Acknowledgements 51 References 51 COATVANOORD1 24-91CDXC 11. LIST OF FIGURES Figure Page The Compressive Strength of Strong Ceramics: Microplasticity Versus

On Healable Polymers and Fiber-Reinforced Composites

NASA Astrophysics Data System (ADS)

Nielsen, Christian Eric

Polymeric materials capable of healing damage would be valuable in structural applications where access for repair is limited. Approaches to creating such materials are reviewed, with the present work focusing on polymers with thermally reversible covalent cross-links. These special cross-links are Diels-Alder (DA) adducts, which can be separated and re-formed, enabling healing of mechanical damage at the molecular level. Several DA-based polymers, including 2MEP4FS, are mechanically and thermally characterized. The polymerization reaction of 2MEP4FS is modeled and the number of established DA adducts is associated with the glass transition temperature of the polymer. The models are applied to concentric cylinder rotational measurements of 2MEP4FS prepolymer at room and elevated temperatures to describe the viscosity as a function of time, temperature, and conversion. Mechanical damage including cracks and scratches are imparted in cured polymer samples and subsequently healed. Damage due to high temperature thermal degradation is observed to not be reversible. The ability to repair damage without flowing polymer chains makes DA-based healable polymers particularly well-suited for crack healing. The double cleavage drilled compression (DCDC) fracture test is investigated as a useful method of creating and incrementally growing cracks in a sample. The effect of sample geometry on the fracture behavior is experimentally and computationally studied. Computational and empirical models are developed to estimate critical stress intensity factors from DCDC results. Glass and carbon fiber-reinforced composites are fabricated with 2MEP4FS as the matrix material. A prepreg process is developed that uses temperature to control the polymerization rate of the monomers and produce homogeneous prepolymer for integration with a layer of unidirectional fiber. Multiple prepreg layers are laminated to form multi-layered cross-ply healable composites, which are characterized in bending using dynamic mechanical analysis (DMA). Simple, theory-based analyses indicate that numerous cracks are present before testing due to thermal expansion mismatches, and during testing, these cracks must be healing. Extending healable composites to include healable fiber-matrix interfaces is discussed as future work and interfacial healing characterization approaches are considered.

Thiol-vinyl systems as shape memory polymers and novel two-stage reactive polymer systems

NASA Astrophysics Data System (ADS)

Nair, Devatha P.

2011-12-01

The focus of this research was to formulate, characterize and tailor the reaction methodologies and material properties of thiol-vinyl systems to develop novel polymer platforms for a range of engineering applications. Thiol-ene photopolymers were demonstrated to exhibit several advantageous characteristics for shape memory polymer systems for a range of biomedical applications. The thiol-ene shape memory polymer systems were tough and flexible as compared to the acrylic control systems with glass transition temperatures between 30 and 40 °C; ideal for actuation at body temperature. The thiol-ene polymers also exhibited excellent shape fixity and a rapid and distinct shape memory actuation response along with free strain recoveries of greater than 96% and constrained stress recoveries of 100%. Additionally, two-stage reactive thiol-acrylate systems were engineered as a polymer platform technology enabling two independent sets of polymer processing and material properties. There are distinct advantages to designing polymer systems that afford two distinct sets of material properties -- an intermediate polymer that would enable optimum handling and processing of the material (stage 1), while maintaining the ability to tune in different, final properties that enable the optimal functioning of the polymeric material (stage 2). To demonstrate the range of applicability of the two-stage reactive systems, three specific applications were demonstrated; shape memory polymers, lithographic impression materials, and optical materials. The thiol-acrylate reactions exhibit a wide range of application versatility due to the range of available thiol and acrylate monomers as well as reaction mechanisms such as Michael Addition reactions and free radical polymerizations. By designing a series of non-stoichiometeric thiol-acrylate systems, a polymer network is initially formed via a base catalyzed 'click' Michael addition reaction. This self-limiting reaction results in a Stage 1 polymer with excess acrylic functional groups within the network. At a later point in time, the photoinitiated, free radical polymerization of the excess acrylic functional groups results in a highly crosslinked, robust material system. By varying the monomers within the system as well as the stoichiometery of thiol to acrylate functional groups, the ability of the two-stage reactive systems to encompass a wide range of properties at the end of both the stage 1 and stage 2 polymerizations was demonstrated. The thiol-acrylate networks exhibited intermediate Stage 1 rubbery moduli and glass transition temperatures that range from 0.5 MPa and -10 ºC to 22 MPa and 22 ºC respectively. The same polymer networks can then attain glass transition temperatures that range from 5 ºC to 195 ºC and rubbery moduli of up to 200 MPa after the subsequent photocure stage. Two-stage reactive polymer composite systems were also formulated and characterized for thermomechanical and mechanical properties. Thermomechanical analysis showed that the fillers resulted in a significant increase in the modulus at both stage 1 and stage 2 polymerizations without a significant change in the glass transition temperatures (Tg). The two-stage reactive matrix composite formed with a hexafunctional acrylate matrix and 20 volume % silica particles showed a 125% increase in stage 1 modulus and 101% increase in stage 2 modulus, when compared with the modulus of the neat matrix. Finally, the two-stage reactive polymeric devices were formulated and designed as orthopedic suture anchors for arthroscopic surgeries and mechanically characterized. The Stage 1 device was designed to exhibit properties ideal for arthroscopic delivery and device placement with glass transition temperatures 25 -- 30 °C and rubbery moduli ˜ 95 MPa. The subsequent photopolymerization generated Stage 2 polymers designed to match the local bone environment with moduli ranging up to 2 GPa. Additionally, pull-out strengths of 140 N were demonstrated and are equivalent to the pull-strengths achieved by other commercially available suture anchors.

Electrical condition monitoring method for polymers

DOEpatents

Watkins, Jr., Kenneth S.; Morris, Shelby J [Hampton, VA; Masakowski, Daniel D [Worcester, MA; Wong, Ching Ping [Duluth, GA; Luo, Shijian [Boise, ID

2008-08-19

An electrical condition monitoring method utilizes measurement of electrical resistivity of an age sensor made of a conductive matrix or composite disposed in a polymeric structure such as an electrical cable. The conductive matrix comprises a base polymer and conductive filler. The method includes communicating the resistivity to a measuring instrument and correlating resistivity of the conductive matrix of the polymeric structure with resistivity of an accelerated-aged conductive composite.

Plastic scintillators with high loading of one or more metal carboxylates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cherepy, Nerine; Sanner, Robert Dean

According to one embodiment, a method includes incorporating a metal carboxylate complex into a polymeric matrix to form an optically transparent material. According to another embodiment, a material includes at least one metal carboxylate complex incorporated into a polymeric matrix, where the material is optically transparent.

Experimental and theoretical investigation of HT-S/PMR-PI composites for application to advanced aircraft engines. [High-Tip-Speed/Polymerization of Monomeric Reactant

NASA Technical Reports Server (NTRS)

Hanson, M. P.; Chamis, C. C.

1974-01-01

A combined experimental and theoretical investigation was performed in order to: (1) demonstrate that high quality angleplied laminates can be made from HT-S/PMR-PI (PMR in situ polymerization of monomeric reactants), (2) characterize the PMR-PI material and to determine the HT-S unidirectional composite properties required for composite micro and macromechanics and laminate analyses, (3) select HT-S/PMR laminate configurations to meet the general design requirements for high-tip-speed compressor blades. The results of the investigation showed that: HT-S/PMR laminate configurations can be fabricated which satisfy the high-tip-speed compressor blade design requirements when operating within the temperature capability of the polymide matrix.

Atmospheric-Pressure Cold Plasmas Used to Embed Bioactive Compounds in Matrix Material for Active Packaging of Fruits and Vegetables

NASA Astrophysics Data System (ADS)

Fernandez, Sulmer; Pedrow, Patrick; Powers, Joseph; Pitts, Marvin

2009-10-01

Active thin film packaging is a technology with the potential to provide consumers with new fruit and vegetable products-if the film can be applied without deactivating bioactive compounds.Atmospheric pressure cold plasma (APCP) processing can be used to activate monomer with concomitant deposition of an organic plasma polymerized matrix material and to immobilize a bioactive compound all at or below room temperature.Aims of this work include: 1) immobilize an antimicrobial in the matrix; 2) determine if the antimicrobial retains its functionality and 3) optimize the reactor design.The plasma zone will be obtained by increasing the voltage on an electrode structure until the electric field in the feed material (argon + monomer) yields electron avalanches. Results will be described using Red Delicious apples.Prospective matrix precursors are vanillin and cinnamic acid.A prospective bioactive compound is benzoic acid.

Desorption of Hg(II) and Sb(V) on extracellular polymeric substances: effects of pH, EDTA, Ca(II) and temperature shocks.

PubMed

Zhang, Daoyong; Lee, Duu-Jong; Pan, Xiangliang

2013-01-01

Extracellular polymeric substances (EPS) existed ubiquitously in biological systems affect the mobility and availability of heavy metals in the environments. The adsorption-desorption behaviors of Hg(II) and Sb(V) on EPS were investigated. The sorption rates follow Sb(V) > Hg(II), and the desorption rates follow reverse order. Applications of ethylene diamine tetraacetic acid (EDTA), Ca(II) and pH shocks affect desorption rates and desorbed quantities of Hg(II) from EPS-Hg complex. Temperature shock minimally affects the desorption rate of Hg(II). Conversely, the EPS-Sb complex is stable subjected to EDTA, Ca(II), temperature or pH shocks. The excitation-emission matrix (EEM) fluorescence spectroscopy and fast-Fourier (FT-IR) analysis showed that Hg(II) and Sb(V) principally interacted with polysaccharides and protein-like compounds in the EPS, respectively. The EPS-Hg complex presents a time bomb that may release high levels of Hg(II) in short time period under environmental shocks. Copyright © 2012 Elsevier Ltd. All rights reserved.

Thermal analysis of hydroxypropylmethylcellulose and methylcellulose: powders, gels and matrix tablets.

PubMed

Ford, J L

1999-03-15

This review focuses on the thermal analysis of hydroxypropylmethylcellulose (HPMC) and methylcellulose. Differential scanning calorimetry (DSC) of their powders is used to determine temperatures of moisture loss (in conjunction with thermogravimetric analysis) and glass transition temperatures. However, sample preparation and encapsulation affect the values obtained. The interaction of these cellulose ethers with water is evaluated by DSC. Water is added to the powder directly in DSC pans or preformed gels can be evaluated. Data quality depends on previous thermal history but estimates of the quantity of water bound to the polymers may be made. Water uptake by cellulose ethers may be evaluated by the use of polymeric wafers and by following loss of free water, over a series of timed curves, into wafers in contact with water. Cloud points, which assess the reduction of polymer solubility with increase of temperature, may be assessed spectrophotometrically. DSC and rheometric studies are used to follow thermogelation, a process involving hydrophobic interaction between partly hydrated polymeric chains. The advantages and disadvantages of the various methodologies are highlighted. Copyright.

The effects of stress and physical aging on the creep compliance of a polymeric composite

NASA Technical Reports Server (NTRS)

Gates, Thomas E.; Feldman, Mark

1993-01-01

An experimental study was performed to determine the effects of stress and physical aging on the matrix dominated viscoelastic properties of IM7/8320, a high temperature fiber reinforced thermoplastic composite. Established creep/aging test techniques developed for polymers were adapted for testing of the composite material. The transverse and shear compliance for an orthotropic plate were found from creep compliance measurements at constant, sub-Tg temperatures. These compliance terms were shown to be effected by physical aging. Aging time shift factors and shift rates were found to be a function of applied stress.

Composite Polymeric Membranes with Directionally Embedded Fibers for Controlled Dual Actuation.

PubMed

Liu, Li; Bakhshi, Hadi; Jiang, Shaohua; Schmalz, Holger; Agarwal, Seema

2018-04-20

In this paper, preparation method and actuation properties of an innovative composite membrane composed of thermo- and pH-responsive poly(N-isopropylacrylamide-co-acrylic acid) fibers (average diameter ≈ 905 nm) embedded within a passive thermoplastic polyurethane (TPU) matrix at different angles with degree of alignment as high as 98% are presented. The composite membrane has a gradient of TPU along the thickness. It has the capability of temperature- and pH-dependent direction-, and size-controlled actuation in few minutes. The stresses generated at the responsive fiber and nonresponsive matrix provide actuation, whereas the angle at which fibers are embedded in the matrix controls the actuation direction and size. The temperature has no effect on actuation and actuated forms at pH 7 and above, whereas the size of the actuated forms can be controlled by the temperature at lower pH. The membranes are strong enough to reversibly lift and release ≈426 times weight of their own mass (2.47 g metal ring is lifted by a 5.8 mg membrane). Soft actuators are of interest as smart scaffolds, robotics, catalysis, drug release, energy storage, electrodes, and metamaterials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Processing and properties of fiber reinforced polymeric matrix composites: I. IM7/LARC(TM)-PETI-7 polyimide composites

NASA Technical Reports Server (NTRS)

Hou, Tan-Hung

1995-01-01

A phenylethynyl terminated imide oligomer formed from the reaction of benzophenone tetracarboxylic acid dianhydride, an 75:25 molar ratio of 4,4'-oxydianiline and meta-phenylenediamine and 4-phenylethynylphthalic anhydride as the endcapper at a theoretical number average molecular weight (Mn) of approximately 3,700 g/mol was evaluated as a composite resin matrix. A glass transition temperature (Tg) of 315 deg C was reached after 250 deg C/1 hr annealing of the matrix resin. Unidirectional prepreg was made by coating an N-methylpyrrolidinone solution of the amide acid oligomer onto unsized IM7 graphite fibers. The thermal and rheological properties and the solvent/volatile depletion rates of the amide acid/NMP system were determined. This information was used to successfully design a molding cycle for composite fabrication. Composites molded under 800 Psi at 371 C consistently yielded good consolidation as measured by C-scan and optical photomicrography. The composite's short beam shear strength (SBS), longitudinal and transverse flexural strengths and moduli were measured at various temperatures. These composites exhibited excellent room temperature (RT) longitudinal flexural strength and modulus and RT SBS strength retention at 177 C.

Red light accelerates the formation of a human dermal equivalent.

PubMed

Oliveira, Anna Cb; Morais, Thayz Fl; Bernal, Claudia; Martins, Virginia Ca; Plepis, Ana Mg; Menezes, Priscila Fc; Perussi, Janice R

2018-04-01

Development of biomaterials' substitutes and/or equivalents to mimic normal tissue is a current challenge in tissue engineering. Thus, three-dimensional cell culture using type I collagen as a polymeric matrix cell support designed to promote cell proliferation and differentiation was employed to create a dermal equivalent in vitro, as well to evaluate the photobiomodulation using red light. Polymeric matrix cell support was prepared from porcine serous collagen (1.1%) hydrolyzed for 96 h. The biomaterial exhibited porosity of 95%, a median pore of 44 µm and channels with an average distance between the walls of 78 ± 14 µm. The absorption of culture medium was 95%, and the sponge showed no cytotoxicity to Vero cells, a non-tumor cell line. Additionally, it was observed that irradiation with light at 630 nm (fluency 30 J cm -2 ) leads to the cellular photobiomodulation in both monolayer and human dermal equivalent (three-dimensional cell culture system). It was also verified that the cells cultured in the presence of the polymeric matrix cell support, allows differentiation and extracellular matrix secretion. Therefore, the results showed that the collagen sponge used as polymeric matrix cell support and the photobiomodulation at 630 nm are efficient for the production of a reconstructed human dermal equivalent in vitro.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Sang-Woo; Seong, Dong Gi; Yi, Jin-Woo

In order to manufacture carbon fiber-reinforced polyamide-6 (PA-6) composite, we optimized the reactive processing system. The in-situ anionic ring-opening polymerization of ε-caprolactam was utilized with proper catalyst and initiator for PA-6 matrix. The mechanical properties such as tensile strength, inter-laminar shear strength and compressive strength of the produced carbon fiber-reinforced PA-6 composite were measured, which were compared with the corresponding scanning electron microscope (SEM) images to investigate the polymer properties as well as the interfacial interaction between fiber and polymer matrix. Furthermore, kinetics of in-situ anionic ring-opening polymerization of ε-caprolactam will be discussed in the viewpoint of increasing manufacturing speedmore » and interfacial bonding between PA-6 matrix and carbon fiber during polymerization.« less

Effect of polymer type on characterization and filtration performances of multi-walled carbon nanotubes (MWCNT)-COOH-based polymeric mixed matrix membranes.

PubMed

Sengur-Tasdemir, Reyhan; Mokkapati, Venkata R S S; Koseoglu-Imer, Derya Y; Koyuncu, Ismail

2018-05-01

Multi-walled carbon nanotubes (MWCNTs) can be used for the fabrication of mixed matrix polymeric membranes that can enhance filtration perfomances of the membranes by modifying membrane surface properties. In this study, detailed characterization and filtration performances of MWCNTs functionalized with COOH group, blended into polymeric flat-sheet membranes were investigated using different polymer types. Morphological characterization was carried out using atomic force microscopy, scanning electron microscopy and contact angle measurements. For filtration performance tests, protein, dextran, E. coli suspension, Xanthan Gum and real activated sludge solutions were used. Experimental data and analyses revealed that Polyethersulfone (PES) + MWCNT-COOH mixed matrix membranes have superior performance abilities compared to other tested membranes.

On-demand photoinitiated polymerization

DOEpatents

Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

2015-01-13

Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

On-demand photoinitiated polymerization

DOEpatents

Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

2013-12-10

Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

Fabrication of Self-Healable and Patternable Polypyrrole/Agarose Hybrid Hydrogels for Smart Bioelectrodes.

PubMed

Park, Nokyoung; Chae, Seung Chul; Kim, Il Tae; Hur, Jaehyun

2016-02-01

We present a new class of electrically conductive, mechanically moldable, and thermally self-healable hybrid hydrogels. The hybrid gels consist of polypyrrole and agarose as the conductive component and self-healable matrix, respectively. By using the appropriate oxidizing agent under conditions of mild temperature, the polymerization of pyrrole occurred along the three-dimensional network of the agarose hydrogel matrix. In contrast to most commercially available hydrogels, the physical crosslinking of agarose gel allows for reversible gelation in the case of our hybrid gel, which could be manipulated by temperature variation, which controls the electrical on/off behavior of the hybrid gel electrode. Exploiting this property, we fabricated a hybrid conductive hydrogel electrode which also self-heals thermally. The novel composite material we report here will be useful for many technological and biological applications, especially in reactive biomimetic functions and devices, artificial muscles, smart membranes, smart full organic batteries, and artificial chemical synapses.

Disrupting the biofilm matrix improves wound healing outcomes.

PubMed

Wolcott, R

2015-08-01

The most unyielding molecular component of biofilm communities is the matrix structure that it can create around the individual microbes that constitute the biofilm. The type of polymeric substances (polymeric sugars, bacterial proteins, bacterial DNA and even co-opted host substances) are dependent on the microbial species present within the biofilm. The extracellular polymeric substances that make up the matrix give the wound biofilm incredible colony defences against host immunity, host healing and wound care treatments. This polymeric slime layer, which is secreted by bacteria, encases the population of microbes, creating a physical barrier that limits the ingress of treatment agents to the bacteria. The aim of this study was to determine if degrading the wound biofilm matrix would improve wound healing outcomes and if so, if there was a synergy between treating agents that disrupted biofilm defenses with Next Science Wound Gel (wound gel) and cidal agents (topical antibiotics). A three-armed randomised controlled trial was designed to determine if standard of care (SOC) was superior to SOC plus wound gel (SOC + gel) and wound gel alone. The wound gel used in this study contains components that directly attack the biofilm extracellular polymeric substance. The gel was applied directly to the wound bed on a Monday-Wednesday-Friday interval, either alone or with SOC topical antibiotics. Using a surrogate endpoint of 50% reduction in wound volume, the results showed that SOC healed at 53%, wound gel healed at 80%, while SOC plus wound gel showed 93% of wounds being successfully treated. By directly targeting the wound biofilm matrix, wound healing outcomes are improved.

Iron oxide/cassava starch-supported Ziegler-Natta catalysts for in situ ethylene polymerization.

PubMed

Chancharoenrith, Sittikorn; Kamonsatikul, Choavarit; Namkajorn, Montree; Kiatisevi, Supavadee; Somsook, Ekasith

2015-03-06

Iron oxide nanoparticles were used as supporters for in situ polymerization to produce polymer nanocomposites with well-dispersed fillers in polymer matrix. Iron oxide could be sustained as colloidal solutions by cassava starch to produce a good dispersion of iron oxide in the matrix. New supports based on iron oxide/cassava starch or cassava starch for Ziegler-Natta catalysts were utilized as heterogeneous supporters for partially hydrolyzed triethylaluminum. Then, TiCl4 was immobilized on the supports as catalysts for polymerization of ethylene. High-density polyethylene (HDPE) composites were obtained by the synthesized catalysts. A good dispersion of iron oxide/cassava starch particles was observed in the synthesized polymer matrix promoting to good mechanical properties of HDPE. Copyright © 2014 Elsevier Ltd. All rights reserved.

Precision Aliphatic Polyesters with Alternating Microstructures via Cross-Metathesis Polymerization: An Event of Sequence Control.

PubMed

Li, Zi-Long; Zeng, Fu-Rong; Ma, Ji-Mei; Sun, Lin-Hao; Zeng, Zhen; Jiang, Hong

2017-06-01

Sequence-regulated polymerization is realized upon sequential cross-metathesis polymerization (CMP) and exhaustive hydrogenation to afford precision aliphatic polyesters with alternating sequences. This strategy is particularly suitable for the arrangement of well-known monomer units including glycolic acid, lactic acid, and caprolactic acid on polymer chain in a predetermined sequence. First of all, structurally asymmetric monomers bearing acrylate and α-olefin terminuses are generated in an efficient and straightforward fashion. Subsequently, cross-metathesis (co)polymerization of M1 and M2 using the Hoveyda-Grubbs second-generation catalyst (HG-II) furnishes P1-P3, respectively. Finally, hydrogenation yields the desired saturated polyesters HP1-HP3. It is noteworthy that the ε-caprolactone-derived unit is generated in situ rather than introduced to tailor-made monomers prior to CMP. NMR and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) results verify the microstructural periodicity of these precision polyesters. Differential scanning calorimetry (DSC) results reflect that polyesters without methyl side groups exhibit crystallinity, and unsaturated polyester samples show higher glass transition temperatures than their hydrogenated counterparts owing to structural rigidity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrical condition monitoring method for polymers

DOEpatents

Watkins, Jr. Kenneth S.; Morris, Shelby J.; Masakowski, Daniel D.; Wong, Ching Ping; Luo, Shijian

2010-02-16

An electrical condition monitoring method utilizes measurement of electrical resistivity of a conductive composite degradation sensor to monitor environmentally induced degradation of a polymeric product such as insulated wire and cable. The degradation sensor comprises a polymeric matrix and conductive filler. The polymeric matrix may be a polymer used in the product, or it may be a polymer with degradation properties similar to that of a polymer used in the product. The method comprises a means for communicating the resistivity to a measuring instrument and a means to correlate resistivity of the degradation sensor with environmentally induced degradation of the product.

Preparing polymeric matrix composites using an aqueous slurry technique

NASA Technical Reports Server (NTRS)

Johnston, Norman J. (Inventor); Towell, Timothy W. (Inventor)

1993-01-01

An aqueous process was developed to prepare a consolidated composite laminate from an aqueous slurry. An aqueous poly(amic acid) surfactant solution was prepared by dissolving a poly(amic acid) powder in an aqueous ammonia solution. A polymeric powder was added to this solution to form a slurry. The slurry was deposited on carbon fiber to form a prepreg which was dried and stacked to form a composite laminate. The composite laminate was consolidated using pressure and was heated to form the polymeric matrix. The resulting composite laminate exhibited high fracture toughness and excellent consolidation.

High Sensitivity Stress Sensor Based on Hybrid Materials

NASA Technical Reports Server (NTRS)

Cao, Xian-An (Inventor)

2014-01-01

A sensing device is used to detect the spatial distributions of stresses applied by physical contact with the surface of the sensor or induced by pressure, temperature gradients, and surface absorption. The sensor comprises a hybrid active layer that includes luminophores doped in a polymeric or organic host, altogether embedded in a matrix. Under an electrical bias, the sensor simultaneously converts stresses into electrical and optical signals. Among many applications, the device may be used for tactile sensing and biometric imaging.

PMR polyimides: Processable high temperature composite matrix resins

NASA Technical Reports Server (NTRS)

Winters, W. E.; Serafini, T. T.

1975-01-01

Processing reproducibility and versatility were demonstrated for producing addition-cured polyimide/graphite fiber composites using an in situ polymerization of monomeric reactants directly on the fiber surface. The polymers so derived, designated PMR polyimides, can be fabricated into composite structures by laminating, random fiber molding or autoclave curing. Composites were determined to be thermally stable and retain useful properties after extended exposures at 550 F to 650 F. The material and fabrication capability were demonstrated by the fabrication and evaluation of prototype complex fan blades.

PMR polyimides - Processable high temperature composite matrix resins

NASA Technical Reports Server (NTRS)

Winters, W. E.; Serafini, T. T.

1975-01-01

Processing reproducibility and versatility were demonstrated for producing addition-cured polyimide/graphite fiber composites using a unique in situ polymerization of monomeric reactants directly on the fiber surface. The polymers so derived, designated PMR polyimides, can be fabricated into composite structures by laminating, random fiber molding or autoclave curing. Composites were determined to be thermally stable and retain useful properties after extended exposures at 550 to 650 F. The material and fabrication capability were demonstrated by the fabrication and evaluation of prototype complex fan blades.-

Tailor making high performance graphite fiber reinforced PMR polyimides

NASA Technical Reports Server (NTRS)

Serafini, T. T.; Vannucci, R. D.

1974-01-01

Studies performed to demonstrate the feasibility of using the polymerization of monomer reactants (PMR) approach to tailor make processable polyimide matrix resins are described. Monomeric reactant solutions containing the dimethyl ester of 3,3',4,4' -benzophenonetetracarboxylic acid, 4, 4' -methylenedianiline and the monomethyl ester of 5-norbornene-2, 3-dicarboxylic acid were used to impregnate Hercules HTS graphite fiber. Six different monomeric reactant stoichiometries were studied. The processing characteristics and elevated temperature mechanical properties of the PMR polyimide/HTS graphite fiber composites are described.

Crumb waste tire rubber surface modification by plasma polymerization of ethanol and its application on oil-well cement

NASA Astrophysics Data System (ADS)

Xiaowei, Cheng; Sheng, Huang; Xiaoyang, Guo; Wenhui, Duan

2017-07-01

Crumb waste tire rubber (WTR) was pretreated by oxygen low temperature plasma (LTP) and modified by LTP polymerization process of ethanol monomer to improve the adhesion property with oil-well cement matrix and the mechanical properties of cement. The surface properties of modified crumb WTR and the mechanical properties and structures of modified oil-well cement were investigated by means of contact angle measurement, dispersion test, attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), mechanics performance tests, permeability test and scanning electron microscopy (SEM). It was demonstrated that LTP treatment changed both the surface composition and roughness. The contact angle of pretreated crumb WTR dramatically fell from 122° to 34°, and sample with ethanol LPT polymer film decreased even further to 11°. The ATR-FTIR and XPS analysis results demonstrated that hydrophilic groups, such as -COOH, C-OH, and -CHO, were introduced on the WTR surface. The oxygen atomic percent increased from 8.11% to 14.50% and 24.83%. The mechanical properties, porosity and permeability of raw cement were compared to samples modified by untreated crumb WTR, pretreated crumb WTR and ethanol LTP polymerization treated crumb WTR. It was found that after 28 days, the compressive strength of the samples with the untreated crumb WTR decreased to 80% with respect to raw cement. The tensile strength and flexural strength also had a slight reduction compared with the raw cement. On the contrary, after 28 days, the tensile strength of cement modified by LTP polymerization treated WTR increased 11.03% and 13.36%, and the flexural strength increased 9.65% and 7.31%, respectively. A decrease in the compressive strength also occurred but was inconspicuous. A tight interface bonding for ethanol LTP polymerization treated WTR with cement matrix was observed via an SEM image.

UV-Triggered Self-Healing of a Single Robust SiO2 Microcapsule Based on Cationic Polymerization for Potential Application in Aerospace Coatings.

PubMed

Guo, Wanchun; Jia, Yin; Tian, Kesong; Xu, Zhaopeng; Jiao, Jiao; Li, Ruifei; Wu, Yuehao; Cao, Ling; Wang, Haiyan

2016-08-17

UV-triggered self-healing of single microcapsules has been a good candidate to enhance the life of polymer-based aerospace coatings because of its rapid healing process and healing chemistry based on an accurate stoichiometric ratio. However, free radical photoinitiators used in single microcapsules commonly suffer from possible deactivation due to the presence of oxygen in the space environment. Moreover, entrapment of polymeric microcapsules into coatings often involves elevated temperature or a strong solvent, probably leading to swelling or degradation of polymer shell, and ultimately the loss of active healing species into the host matrix. We herein describe the first single robust SiO2 microcapsule self-healing system based on UV-triggered cationic polymerization for potential application in aerospace coatings. On the basis of the similarity of solubility parameters of the active healing species and the SiO2 precursor, the epoxy resin and cationic photoinitiator are successfully encapsulated into a single SiO2 microcapsule via a combined interfacial/in situ polymerization. The single SiO2 microcapsule shows solvent resistance and thermal stability, especially a strong resistance for thermal cycling in a simulated space environment. In addition, the up to 89% curing efficiency of the epoxy resin in 30 min, and the obvious filling of scratches in the epoxy matrix demonstrate the excellent UV-induced healing performance of SiO2 microcapsules, attributed to a high load of healing species within the capsule (up to 87 wt %) and healing chemistry based on an accurate stoichiometric ratio of the photoinitiator and epoxy resin at 9/100. More importantly, healing chemistry based on a UV-triggered cationic polymerization mechanism is not sensitive to oxygen, extremely facilitating future embedment of this single SiO2 microcapsule in spacecraft coatings to achieve self-healing in a space environment with abundant UV radiation and oxygen.

Radiation-induced polymerization of glass-forming systems. IV. Effect of the homogeneity of polymerization phase and polymer concentration on temperature dependence of initial polymerization rate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaetsu, I.; Ito, A.; Hayashi, K.

1973-06-01

The effect of homogeneity of polymerization phase and monomer concentration on the temperature dependence of initial polymerization rate was studied in the radiation-induced radical polymerization of binary systems consisting of glass-forming monomer and solvent. In the polymerization of a completely homogeneous system such as HEMA-propylene glycol, a maximum and a minimum in polymerization rates as a function of temperature, characteristic of the polymerization in glass-forming systems, were observed for all monomer concentrations. However, in the heterogeneous polymerization systems such as HEMA-triacetin and HEMAisoamyl acetate, maximum and minimum rates were observed in monomer-rich compositions but not at low monomer concentrations. Furthermore,more » in the HEMA-dioctyl phthalate polymerization system, which is extremely heterogeneous, no maximum and minimum rates were observed at any monomer concentration. The effect of conversion on the temperature dependence of polymerization rate in homogeneous bulk polymerization of HEMA and GMA was investigated. Maximum and minimum rates were observed clearly in conversions less than 10% in the case of HEMA and less than 50% in the case of GMA, but the maximum and minimum changed to a mere inflection in the curve at higher conversions. A similar effect of polymer concentration on the temperature dependence of polymerization rate in the GMA-poly(methyl methacrylate) system was also observed. It is deduced that the change in temperature dependence of polymerization rate is attributed to the decrease in contribution of mutual termination reaction of growing chain radicals to the polymerization rate. (auth)« less

Ultem((R))/ZIF-8 mixed matrix hollow fiber membranes for CO2/N-2 separations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Y; Johnson, JR; Karvan, O

2012-05-15

Organic-inorganic hybrid (mixed matrix) membranes can potentially extend the separation performance of traditional polymeric materials while maintaining processing convenience. Although many dense films studies have been reported, there have been few reported cases of these materials being successfully extended to asymmetric hollow fibers. In this work we report the first successful production of mixed matrix asymmetric hollow fiber membranes containing metal-organic-framework (MOF) ZIF-8 fillers. Specifically, we have incorporated ZIF-8 into a polyetherimide (Ultem((R)) 1000) matrix and produced dual-layer asymmetric hollow fiber membranes via the dry jet-wet quench method. The outer separating layer of these composite fibers contains 13 wt% (17more » vol%) of ZIF-8 filler. These membranes have been tested over a range of temperatures and pressures for a variety of gas pairs. An increase in separation performance for the CO2/N-2 gas pairs was observed for both pure gas and mixed gas feeds. (C) 2012 Elsevier B.V. All rights reserved.« less

Resin Systems and Chemistry-Degradation Mechanisms and Durability in Long-Term Durability of Polymeric Matrix Composites. Chapter 1

NASA Technical Reports Server (NTRS)

Hinkley, Jeffrey A.; Connell, John W.

2012-01-01

In choosing a polymer-matrix composite material for a particular application, a number of factors need to be weighed. Among these are mechanical requirements, fabrication method (e.g. press-molding, resin infusion, filament winding, tape layup), and use conditions. Primary among the environmental exposures encountered in aerospace structures are moisture and elevated temperatures, but certain applications may require resistance to other fluids and solvents, alkaline agents, thermal cycling, radiation, or rapid, localized heating (for example, lightning strike). In this chapter, the main classes of polymer resin systems found in aerospace composites will be discussed. Within each class, their responses to environmental factors and the associated degradation mechanisms will be reviewed.

Nanophosphor composite scintillators comprising a polymer matrix

DOEpatents

Muenchausen, Ross Edward; Mckigney, Edward Allen; Gilbertson, Robert David

2010-11-16

An improved nanophosphor composite comprises surface modified nanophosphor particles in a solid matrix. The nanophosphor particle surface is modified with an organic ligand, or by covalently bonding a polymeric or polymeric precursor material. The surface modified nanophosphor particle is essentially charge neutral, thereby preventing agglomeration of the nanophosphor particles during formation of the composite material. The improved nanophosphor composite may be used in any conventional scintillator application, including in a radiation detector.

Nanoimages show disruption of tubulin polymerization by chlorpyrifos oxon: Implications for neurotoxicity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grigoryan, Hasmik; Lockridge, Oksana

2009-10-15

Organophosphorus agents cause cognitive deficits and depression in some people. We hypothesize that the mechanism by which organophosphorus agents cause these disorders is by modification of proteins in the brain. One such protein could be tubulin. Tubulin polymerizes to make the microtubules that transport cell components to nerve axons. The goal of the present work was to measure the effect of the organophosphorus agent chlorpyrifos oxon on tubulin polymerization. An additional goal was to identify the amino acids covalently modified by chlorpyrifos oxon in microtubule polymers and to compare them to the amino acids modified in unpolymerized tubulin dimers. Purifiedmore » bovine tubulin (0.1 mM) was treated with 0.005-0.1 mM chlorpyrifos oxon for 30 min at room temperature and then polymerized by addition of 1 mM GTP to generate microtubules. Microtubules were visualized by atomic force microscopy. Chlorpyrifos oxon-modified residues were identified by tandem ion trap electrospray ionization and matrix-assisted laser desorption/ionization mass spectrometry of tryptic peptides. Nanoimaging showed that low concentrations (0.005 and 0.01 mM) of chlorpyrifos oxon yielded short, thin microtubules. A concentration of 0.025 mM stimulated polymerization, while high concentrations (0.05 and 0.1 mM) caused aggregation. Of the 17 tyrosines covalently modified by chlorpyrifos oxon in unpolymerized tubulin dimers, only 2 tyrosines were labeled in polymerized microtubules. The two labeled tyrosines in polymerized tubulin were Tyr 103 in EDAANNY*R of alpha tubulin, and Tyr 281 in GSQQY*R of beta tubulin. In conclusion, chlorpyrifos oxon binding to tubulin disrupts tubulin polymerization. These results may lead to an understanding of the neurotoxicity of organophosphorus agents.« less

Nanoimages show disruption of tubulin polymerization by chlorpyrifos oxon; implications for neurotoxicity

PubMed Central

Grigoryan, Hasmik; Lockridge, Oksana

2009-01-01

Organophosphorus agents cause cognitive deficits and depression in some people. We hypothesize that the mechanism by which organophosphorus agents cause these disorders is by modification of proteins in the brain. One such protein could be tubulin. Tubulin polymerizes to make the microtubules that transport cell components to nerve axons. The goal of the present work was to measure the effect of the organophosphorus agent chlorpyrifos oxon on tubulin polymerization. An additional goal was to identify the amino acids covalently modified by chlorpyrifos oxon in microtubule polymers and to compare them to the amino acids modified in unpolymerized tubulin dimers. Purified bovine tubulin (0.1 mM) was treated with 0.005-0.1 mM chlorpyrifos oxon for 30 min at room temperature and then polymerized by addition of 1 mM GTP to generate microtubules. Microtubules were visualized by atomic force microscopy. Chlorpyrifos oxon-modified residues were identified by tandem ion trap electrospray ionization and matrix-assisted laser desorption/ionization mass spectrometry of tryptic peptides. Nanoimaging showed that low concentrations (0.005 and 0.01 mM) of chlorpyrifos oxon yielded short, thin microtubules. A concentration of 0.025 mM stimulated polymerization, while high concentrations (0.05 and 0.1 mM) caused aggregation. Of the 17 tyrosines covalently modified by chlorpyrifos oxon in unpolymerized tubulin dimers, only 2 tyrosines were labeled in polymerized microtubules. The two labeled tyrosines in polymerized tubulin were Tyr 103 in EDAANNY*R of alpha tubulin, and Tyr 281 in GSQQY*R of beta tubulin. In conclusion, chlorpyrifos oxon binding to tubulin disrupts tubulin polymerization. These results may lead to an understanding of the neurotoxicity of organophosphorus agents. PMID:19631231

Radiation-induced polymerization for the immobilization of penicillin acylase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boccu, E.; Carenza, M.; Lora, S.

The immobilization of Escherichia coli penicillin acylase was investigated by radiation-induced polymerization of 2-hydroxyethyl methacrylate at low temperature. A leak-proof composite that does not swell in water was obtained by adding the cross-linking agent trimethylolpropane trimethacrylate to the monomer-aqueous enzyme mixture. Penicillin acylase, which was immobilized with greater than 70% yield, possessed a higher Km value toward the substrate 6-nitro-3-phenylacetamidobenzoic acid than the free enzyme form (Km = 1.7 X 10(-5) and 1 X 10(-5) M, respectively). The structural stability of immobilized penicillin acylase, as assessed by heat, guanidinium chloride, and pH denaturation profiles, was very similar to that ofmore » the free-enzyme form, thus suggesting that penicillin acylase was entrapped in its native state into aqueous free spaces of the polymer matrix.« less

Exploration of ethyl anthranilate-loaded monolithic matrix-type prophylactic polymeric patch.

PubMed

Islam, Johirul; Zaman, Kamaruz; Chakrabarti, Srijita; Bora, Nilutpal Sharma; Pathak, Manash Pratim; Mandal, Santa; Junejo, Julfikar Ali; Chattopadhyay, Pronobesh

2017-10-01

Compromised stability of pharmaceutical formulations loaded with volatiles is a serious problem associated with devices designed to deliver volatile compounds. The present study has been focused to evaluate the stability potential of matrix-type polymeric patches composed of volatile ethyl anthranilate for prophylaxis against vector-borne diseases. Ethyl anthranilate-loaded matrix-type polymeric patches were fabricated by solvent evaporation method on an impermeable backing membrane and attached to temporary release liners. Stability testing of the polymeric patches was performed as per the International Conference on Harmonization (ICH) guidelines for 6 months under accelerated conditions. In addition, the quantification of residual solvents was also performed as per the ICH guidelines. After conducting the stability studies for 6 months, the optimized patches showed the best possible results with respect to uniformity of drug content, physical appearance, and other analytical parameters. Furthermore, the amount of residual solvent was found well below the accepted limit. Thus, the present report outlined the analytical parameters to be evaluated to ensure the stability of a certain devices consisting of volatile compounds. Copyright © 2016. Published by Elsevier B.V.

Low temperature catalytic oxidative aging of LDPE films in response to heat excitation.

PubMed

Luo, Xuegang; Zhang, Sizhao; Ding, Feng; Lin, Xiaoyan

2015-09-14

The waste treatment of polymer materials is often conducted using the photocatalytic technique; however, complete decomposition is frequently inhibited owing to several shortcomings such as low quantum yield and the requirement of ultraviolet irradiation. Herein, we report a strategy to implement moderate management of polymeric films via thermocatalytic oxidative route, which is responsive to heat stimulus. Diverse LDPE-matrix films together with as-prepared thermal catalysts (TCs) or initiators were synthesized to further investigate heat-dependent-catalytic degradation effects. After artificial ageing, structural textures of the as-synthesized films could be chemically deteriorated, followed by a huge increase in surface roughness values, and appreciable loss was also found in the average molecular weights and mechanical parameters. We found an emergent phenomenon in which crystallization closely resembled two-dimensional (2D) growth, which displayed rod-like or disc-type crystal shapes. New chemical groups generated on film surfaces were monitored, and led to a higher limiting oxygen index because of strong catalytic oxidation, thus demonstrating the success of catalytic oxidative ageing by heat actuation. The underlying mechanism responsible for thermocatalytic oxidative pattern is also discussed. Accordingly, these findings may have important implications for better understanding the development of polymeric-matrix waste disposal.

Polymerization- and Solvent-Induced Phase Separation in Hydrophilic-rich Dentin Adhesive Mimic

PubMed Central

Abedin, Farhana; Ye, Qiang; Good, Holly J; Parthasarathy, Ranganathan; Spencer, Paulette

2014-01-01

Current dental resin undergoes phase separation into hydrophobic-rich and hydrophilic-rich phases during infiltration of the over-wet demineralized collagen matrix. Such phase separation undermines the integrity and durability of the bond at the composite/tooth interface. This study marks the first time that the polymerization kinetics of model hydrophilic-rich phase of dental adhesive has been determined. Samples were prepared by adding varying water content to neat resins made from 95 and 99wt% hydroxyethylmethacrylate (HEMA) and 5 and 1wt% (2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl1]-propane (BisGMA) prior to light curing. Viscosity of the formulations decreased with increased water content. The photo-polymerization kinetics study was carried out by time-resolved FTIR spectrum collector. All of the samples exhibited two-stage polymerization behavior which has not been reported previously for dental resin formulation. The lowest secondary rate maxima were observed for water content of 10-30%wt. Differential scanning calorimetry (DSC) showed two glass transition temperatures for the hydrophilic-rich phase of dental adhesive. The DSC results indicate that the heterogeneity within the final polymer structure decreased with increased water content. The results suggest a reaction mechanism involving both polymerization-induced phase separation (PIPs) and solvent-induced phase separation (SIPs) for the model hydrophilic-rich phase of dental resin. PMID:24631658

The effect of pigment matrix, temperature and amount of carrier on the yield and final color properties of spray dried purple corn (Zea mays L.) cob anthocyanin powders.

PubMed

Lao, Fei; Giusti, M Monica

2017-07-15

Spray drying is an economic technique to produce anthocyanin-based colorants. High pigments yields with minimum color degradation are desirable to maximize quality and profits. This study evaluated the impacts of purple corncob (PCC) anthocyanin extraction matrices (hot water, 40% ethanol, C18 purified), drying inlet temperature (130, 150, 170°C) and amount of carrier (2%, 5%, 10% maltodextrin) on the yields and quality of PCC anthocyanin powders. Monomeric and polymeric anthocyanins, color properties (CIELch, haze), and pigments composition before and after spray drying were determined. The yield and final color quality of spray dried PCC anthocyanins were affected (p<0.05) by all parameters evaluated. The pigment matrix, inlet temperature, and carrier amount had biggest impacts on product water solubility, pigments degradation and yield, respectively. The optimal combination of hot water extracts spray dried with 5% maltodextrin at 150°C gave the highest pigment yield (∼90%) with good solubility with the least color loss. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of Mg content on the thermal stability and mechanical behaviour of PLLA/Mg composites processed by hot extrusion.

PubMed

Cifuentes, S C; Lieblich, M; López, F A; Benavente, R; González-Carrasco, J L

2017-03-01

In the field of bioabsorbable composites for biomedical applications, extrusion has been employed as a method to prepare homogeneous blends of polymeric matrices with bioactive ceramic fillers. In this work, the suitability of processing poly-l-lactic acid/Magnesium (PLLA/Mg) composites by hot extrusion has been assessed by a systematic characterization of PLLA/Mg composites containing different amounts of Mg particles up to 7wt%. The results show that extrusion causes a reduction of almost 20% in the viscosity average molecular weight of PLLA, which further decreases with increasing Mg content. Extrusion gave always rise to a homogeneous distribution of Mg particles within the PLLA matrix. This composite processing was not compromised by the degradation of the polymeric matrix because the processing temperature was always below the onset degradation temperature. In the processing conditions employed in the present work, degradation of the composite slightly increases as more Mg is added up to 5wt%, but is very high at 7wt%. This was also evident from the mechanical behaviour, so that Mg particles improved the stiffness and compression strength of neat PLLA until 5wt% of Mg content, which dropped drastically when the material had 7wt% of Mg. The filler strengthening factor decreases with the increment in Mg content. In order to obtain an optimised contribution of Mg particles, a balance between thermal degradation and mechanical resistance of PLLA must be achieved. Copyright © 2016 Elsevier B.V. All rights reserved.

Thermal effect on structure organizations in cobalt-fullerene nanocomposition.

PubMed

Lavrentiev, Vasily; Vacik, Jiri; Naramoto, Hiroshi; Sakai, Seiji

2010-04-01

Effect of deposition temperature (Ts) on structure of Co-C60 nanocomposite (NC) prepared by simultaneous deposition of cobalt and fullerene on sapphire is presented. The NC structure variations with Ts increasing from room temperature (RT) to 400 degrees C have been analyzed using scanning electron microscopy (SEM), atomic force microscopy (AFM) and Raman spectroscopy. AFM and SEM show granule-like structure of the Co-C60 film. The mixture film deposited at RT includes the hills on the surface suggesting accumulation of internal stress during phase separation. Raman spectra show 25 cm(-1) downshift of Ag(2) C60 peak suggesting -Co-C60- polymerization in C60-based matrix of the NC film. Analysis of Raman spectra has revealed existence of amorphous carbon (a-C) in the NC matrix that argues C60 decomposition. The Ts increase to 200 degrees C causes the surface hills smoothing. In parallel, downshift of the Ag(2) peak decreases to 16 cm(-1) that implies more pronounced phase separation and lower -Co-C60- polymerization efficiency. Also, amount of a-C content slightly increases. Further Ts increasing to 400 degrees C changes the NC structure dramatically. AFM shows evident enlargement of the granules. According to Raman spectra the high Ts deposition yields pronounced C60 decomposition increasing the a-C content. Features of a-C Raman peak imply nucleation of graphitic islands at the NC interfaces. Abundant decomposition of C60 in the mixture film deposited at 400 degrees C is referred to cobalt catalytic effect.

[Modern polymers in matrix tablets technology].

PubMed

Zimmer, Łukasz; Kasperek, Regina; Poleszak, Ewa

2014-01-01

Matrix tablets are the most popular method of oral drug administration, and polymeric materials have been used broadly in matrix formulations to modify and modulate drug release rate. The main goal of the system is to extend drug release profiles to maintain a constant in vivo plasma drug concentration and a consistent pharmacological effect. Polymeric matrix tablets offer a great potential as oral controlled drug delivery systems. Cellulose derivatives, like hydroxypropyl methylcellulose (HPMC) are often used as matrix formers. However, also other types of polymers can be used for this purpose including: Kollidon SR, acrylic acid polymers such as Eudragits and Carbopols. Nevertheless, polymers of natural origin like: carragens, chitosan and alginates widely used in the food and cosmetics industry are now coming to the fore of pharmaceutical research and are used in matrix tablets technology. Modern polymers allow to obtain matrix tablets by 3D printing, which enables to develop new formulation types. In this paper, the polymers used in matrix tablets technology and examples of their applications were described.

Nanocellular foam with solid flame retardant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Liang; Kelly-Rowley, Anne M.; Bunker, Shana P.

Prepare nanofoam by (a) providing an aqueous solution of a flame retardant dissolved in an aqueous solvent, wherein the flame retardant is a solid at 23.degree. C. and 101 kiloPascals pressure when in neat form; (b) providing a fluid polymer composition selected from a solution of polymer dissolved in a water-miscible solvent or a latex of polymer particles in a continuous aqueous phase; (c) mixing the aqueous solution of flame retardant with the fluid polymer composition to form a mixture; (d) removing water and, if present, solvent from the mixture to produce a polymeric composition having less than 74 weight-percentmore » flame retardant based on total polymeric composition weight; (e) compound the polymeric composition with a matrix polymer to form a matrix polymer composition; and (f) foam the matrix polymer composition into nanofoam having a porosity of at least 60 percent.« less

Fabrication of polyimide-based nanocomposites containing functionalized graphene oxide nanosheets by in-situ polymerization and their properties

NASA Astrophysics Data System (ADS)

Qian, Yong; Lan, Yanfei; Xu, Jianping; Ye, Fucheng; Dai, Shizhen

2014-09-01

In this study, a facile and effective strategy is proposed to fabricate polyimide (PI)-based nanocomposites containing functionalized graphene oxide (FGO) nanosheets by in-situ polymerization and thermal imidization. Highly dispersed CIGO which was firstly obtained by graphene oxide (GO) functionalized with cyclohexyl isocyanate (CI) exhibited excellent dispersibility and compatibility in polyamic acid (PAA, precursor of PI) matrix via in-situ polymerization. Then the CIGO sheets were partially thermally reduced efficiently to FGO during the thermal imidization process of PAA. The incorporation of FGO sheets significantly affected the macroscopic properties of the PI-based composites. A 56.5% increase in the tensile strength and a 43.8% improvement in the Young's modulus were achieved for 2.0 wt% FGO loading. Furthermore, the thermal stability and glass transition temperature (Tg) were improved by adding FGO. In addition, the hydrophobic behavior of the PI-FGO composite clearly improved because of the excellent hydrophobic properties of FGO. The success of this approach provides a good rational for developing high-performance polymer-based composite materials.

Metallization of Various Polymers by Cold Spray

NASA Astrophysics Data System (ADS)

Che, Hanqing; Chu, Xin; Vo, Phuong; Yue, Stephen

2018-01-01

Previous results have shown that metallic coatings can be successfully cold sprayed onto polymeric substrates. This paper studies the cold sprayability of various metal powders on different polymeric substrates. Five different substrates were used, including carbon fiber reinforced polymer (CFRP), acrylonitrile butadiene styrene (ABS), polyether ether ketone (PEEK), polyethylenimine (PEI); mild steel was also used as a benchmark substrate. The CFRP used in this work has a thermosetting matrix, and the ABS, PEEK and PEI are all thermoplastic polymers, with different glass transition temperatures as well as a number of distinct mechanical properties. Three metal powders, tin, copper and iron, were cold sprayed with both a low-pressure system and a high-pressure system at various conditions. In general, cold spray on the thermoplastic polymers rendered more positive results than the thermosetting polymers, due to the local thermal softening mechanism in the thermoplastics. Thick copper coatings were successfully deposited on PEEK and PEI. Based on the results, a method is proposed to determine the feasibility and deposition window of cold spraying specific metal powder/polymeric substrate combinations.

Synthesis and characterization of polymeric V2O5/AlO(OH) with nanopores on alumina support.

PubMed

Ahmad, A L; Abd Shukor, S R; Leo, C P

2006-12-01

Polymeric vanadium pentoxide gel was formed via the reaction of V2O5 powder with hydrogen peroxide. The polymeric vanadium pentoxide gel was then dispersed in alumina gel. Different vanadium loading composites were coated on alumina support and calcined at 500 degrees C for 1 hr. These composite layers were characterized using TGA, FT-IR, XRD, SEM, and Autosorb. It was found that the lamellar structure of polymerized vanadium pentoxide was retained in the inorganic matrix. Crystalline alumina in gamma phase was formed after calcinations. However, the vanadium-alumina mixed oxides are lack of the well defined PXRD peaks for polycrystalline V2O5. This is possibly because the vanadia species are highly dispersed in the alumina matrix or the vanadia species are dispersed as crystalline which is smaller than 4 nm. In addition, the imbedded polymeric vanadium oxide improved the specific area and average pore diameter of the composite layer.

Method for nanoencapsulation of aerogels and nanoencapsulated aerogels produced by such method

NASA Technical Reports Server (NTRS)

Sullivan, Thomas A. (Inventor)

2007-01-01

A method for increasing the compressive modulus of aerogels comprising: providing aerogel substrate comprising a bubble matrix in a chamber; providing monomer to the chamber, the monomer comprising vapor phase monomer which polymerizes substantially free of polymerization byproducts; depositing monomer from the vapor phase onto the surface of the aerogel substrate under deposition conditions effective to produce a vapor pressure sufficient to cause the vapor phase monomer to penetrate into the bubble matrix and deposit onto the surface of the aerogel substrate, producing a substantially uniform monomer film; and, polymerizing the substantially uniform monomer film under polymerization conditions effective to produce polymer coated aerogel comprising a substantially uniform polymer coating substantially free of polymerization byproducts.Polymer coated aerogel comprising aerogel substrate comprising a substantially uniform polymer coating, said polymer coated aerogel comprising porosity and having a compressive modulus greater than the compressive modulus of the aerogel substrate, as measured by a 100 lb. load cell at 1 mm/minute in the linear range of 20% to 40% compression.

Influence of gamma irradiation on polymerization of pyrrole and glucose oxidase immobilization onto poly (pyrrole)/poly (vinyl alcohol) matrix

NASA Astrophysics Data System (ADS)

Idris, Sarada; A. Bakar, Ahmad Ashrif; Thevy Ratnam, Chantara; Kamaruddin, Nur Hasiba; Shaari, Sahbudin

2017-04-01

This paper describes the immobilization of glucose oxidase, GOx onto polymer matrix comprising of poly(pyrrole), PPy and poly(vinyl alcohol), PVA using gamma irradiation technique. Py/PVA-GOx film was prepared by spreading PVA:GOx, 1:1 solution onto dried pyrrole film and exposed to gamma irradiation from cobalt 60 source at doses ranging from 0 to 60 kGy. The films were subjected to structural and morphological analyses by using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Scanning electron microscope (SEM), Field emission scanning electron microscope (FESEM) and Atomic-force microscopy (AFM) techniques. Similar studies were also made on pristine pyrrole film which served as control. The SEM and FTIR spectra of Py/PVA-GOx film revealed that pyrrole has been successfully polymerized through irradiation-induced reactions. The results on the morphological properties of the samples characterize using FESEM, SEM and AFM further confirmed the occurrence of radiation-induced modification of Py/PVA-GOx film. The FTIR spectra showed the existence of intermolecular interaction between polymer matrix and GOx indicating that GOx had been successfully immobilized onto Ppy/PVA matrix by radiation-induced reactions. Results revealed that radiation induced reactions such as polymerization of pyrrole, crosslinking of PVA, grafting between the adjacent PVA and pyrrole molecules as well as immobilization of GOx onto Ppy/PVA matrix occurred simultaneously upon gamma irradiation. The optimum dose for GOx immobilization in the polymer matrix found to be 40 kGy. Therefore it is clear that this irradiation technique offered a simple single process to produce Py/PVA-GOx film without additional crosslinking and polymerization agents.

Tensile Properties of Polymeric Matrix Composites Subjected to Cryogenic Environments

NASA Technical Reports Server (NTRS)

Whitley, Karen S.; Gates, Thomas S.

2004-01-01

Polymer matrix composites (PMC s) have seen limited use as structural materials in cryogenic environments. One reason for the limited use of PMC s in cryogenic structures is a design philosophy that typically requires a large, validated database of material properties in order to ensure a reliable and defect free structure. It is the intent of this paper to provide an initial set of mechanical properties developed from experimental data of an advanced PMC (IM7/PETI-5) exposed to cryogenic temperatures and mechanical loading. The application of this data is to assist in the materials down-select and design of cryogenic fuel tanks for future reusable space vehicles. The details of the material system, test program, and experimental methods will be outlined. Tension modulus and strength were measured at room temperature, -196 C, and -269 C on five different laminates. These properties were also tested after aging at -186 C with and without loading applied. Microcracking was observed in one laminate.

Prospects for using carbon-carbon composites for EMI shielding

NASA Technical Reports Server (NTRS)

Gaier, James R.

1990-01-01

Since pyrolyzed carbon has a higher electrical conductivity than most polymers, carbon-carbon composites would be expected to have higher electromagnetic interference (EMI) shielding ability than polymeric resin composites. A rule of mixtures model of composite conductivity was used to calculate the effect on EMI shielding of substituting a pyrolyzed carbon matrix for a polymeric matrix. It was found that the improvements were small, no more than about 2 percent for the lowest conductivity fibers (ex-rayon) and less than 0.2 percent for the highest conductivity fibers (vapor grown carbon fibers). The structure of the rule of mixtures is such that the matrix conductivity would only be important in those cases where it is much higher than the fiber conductivity, as in metal matrix composites.

Silyl Ketene Acetals/B(C₆F₅)₃ Lewis Pair-Catalyzed Living Group Transfer Polymerization of Renewable Cyclic Acrylic Monomers.

PubMed

Hu, Lu; Zhao, Wuchao; He, Jianghua; Zhang, Yuetao

2018-03-15

This work reveals the silyl ketene acetal (SKA)/B(C₆F₅)₃ Lewis pair-catalyzed room-temperature group transfer polymerization (GTP) of polar acrylic monomers, including methyl linear methacrylate (MMA), and the biorenewable cyclic monomers γ-methyl-α-methylene-γ-butyrolactone (MMBL) and α-methylene-γ-butyrolactone (MBL) as well. The in situ NMR monitored reaction of SKA with B(C₆F₅)₃ indicated the formation of Frustrated Lewis Pairs (FLPs), although it is sluggish for MMA polymerization, such a FLP system exhibits highly activity and living GTP of MMBL and MBL. Detailed investigations, including the characterization of key reaction intermediates, polymerization kinetics and polymer structures have led to a polymerization mechanism, in which the polymerization is initiated with an intermolecular Michael addition of the ester enolate group of SKA to the vinyl group of B(C₆F₅)₃-activated monomer, while the silyl group is transferred to the carbonyl group of the B(C₆F₅)₃-activated monomer to generate the single-monomer-addition species or the active propagating species; the coordinated B(C₆F₅)₃ is released to the incoming monomer, followed by repeated intermolecular Michael additions in the subsequent propagation cycle. Such neutral SKA analogues are the real active species for the polymerization and are retained in the whole process as confirmed by experimental data and the chain-end analysis by matrix-assisted laser desorption/ionization time of flight mass spectroscopy (MALDI-TOF MS). Moreover, using this method, we have successfully synthesized well-defined PMMBL- b -PMBL, PMMBL- b -PMBL- b -PMMBL and random copolymers with the predicated molecular weights ( M n ) and narrow molecular weight distribution (MWD).

Rapid Engineering of Three-Dimensional, Multicellular Tissues With Polymeric Scaffolds

NASA Technical Reports Server (NTRS)

Gonda, Steve R.; Jordan, Jacqueline; Fraga, Denise N.

2007-01-01

A process has been developed for the rapid tissue engineering of multicellular-tissue-equivalent assemblies by the controlled enzymatic degradation of polymeric beads in a low-fluid-shear bioreactor. In this process, the porous polymeric beads serve as temporary scaffolds to support the assemblies of cells in a tissuelike 3D configuration during the critical initial growth phases of attachment of anchorage-dependent cells, aggregation of the cells, and formation of a 3D extracellular matrix. Once the cells are assembled into a 3D array and enmeshed in a structural supportive 3D extracellular matrix (ECM), the polymeric scaffolds can be degraded in the low-fluid-shear environment of the NASA-designed bioreactor. The natural 3D tissuelike assembly, devoid of any artificial support structure, is maintained in the low-shear bioreactor environment by the newly formed natural cellular/ECM. The elimination of the artificial scaffold allows normal tissue structure and function.

Effect of initial temperature and concentration of catalyst in polyeugenol production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Widayat, E-mail: yayat-99@yahoo.com; Center of Biomass and Renewable Energy Center of Research and Service Diponegoro University Jln Prof. Soedarto, SH. Semarang 50 239, Tel / Fax:; Fatuchrohman, Alviano

2015-12-29

Objective of this research to study influencing of sulfuric acid concentration and initials temperature on polymerization of eugenol. Eugenol is the largest compound in the clove oil that used as raw material. Eugenol was polymerized laboratory scale. Polymerization processing conducted in reactor at 30 minutes. Polyeugenol was obtained in polymerization was conducted at temperature 40°C and ratio eugenol to sulfuric acid 1:15 mole. This research was pbtained the highest yield 81.49%. However, the weight would be increase in according with increasing of initial temperature. The polymerization in temperature 50°C with 1:1.5 mole ratio has the heaviest molecule weight; 47,530.76 gr/mole.

Rapid profiling of polymeric phenolic acids in Salvia miltiorrhiza by hybrid data-dependent/targeted multistage mass spectrometry acquisition based on expected compounds prediction and fragment ion searching.

PubMed

Shen, Yao; Feng, Zijin; Yang, Min; Zhou, Zhe; Han, Sumei; Hou, Jinjun; Li, Zhenwei; Wu, Wanying; Guo, De-An

2018-04-01

Phenolic acids are the major water-soluble components in Salvia miltiorrhiza (>5%). According to previous studies, many of them contribute to the cardiovascular effects and antioxidant effects of S. miltiorrhiza. Polymeric phenolic acids can be considered as the tanshinol derived metabolites, e.g., dimmers, trimers, and tetramers. A strategy combined with tanshinol-based expected compounds prediction, total ion chromatogram filtering, fragment ion searching, and parent list-based multistage mass spectrometry acquisition by linear trap quadropole-orbitrap Velos mass spectrometry was proposed to rapid profile polymeric phenolic acids in S. miltiorrhiza. More than 480 potential polymeric phenolic acids could be screened out by this strategy. Based on the fragment information obtained by parent list-activated data dependent multistage mass spectrometry acquisition, 190 polymeric phenolic acids were characterized by comparing their mass information with literature data, and 18 of them were firstly detected from S. miltiorrhiza. Seven potential compounds were tentatively characterized as new polymeric phenolic acids from S. miltiorrhiza. This strategy facilitates identification of polymeric phenolic acids in complex matrix with both selectivity and sensitivity, which could be expanded for rapid discovery and identification of compounds from complex matrix. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amorphous silicon thin film transistor active-matrix organic light-emitting diode displays fabricated on flexible substrates

NASA Astrophysics Data System (ADS)

Nichols, Jonathan A.

Organic light-emitting diode (OLED) displays are of immense interest because they have several advantages over liquid crystal displays, the current dominant flat panel display technology. OLED displays are emissive and therefore are brighter, have a larger viewing angle, and do not require backlights and filters, allowing thinner, lighter, and more power efficient displays. The goal of this work was to advance the state-of-the-art in active-matrix OLED display technology. First, hydrogenated amorphous silicon (a-Si:H) thin film transistor (TFT) active-matrix OLED pixels and arrays were designed and fabricated on glass substrates. The devices operated at low voltages and demonstrated that lower performance TFTs could be utilized in active-matrix OLED displays, possibly allowing lower cost processing and the use of polymeric substrates. Attempts at designing more control into the display at the pixel level were also made. Bistable (one bit gray scale) active-matrix OLED pixels and arrays were designed and fabricated. Such pixels could be used in novel applications and eventually help reduce the bandwidth requirements in high-resolution and large-area displays. Finally, a-Si:H TFT active-matrix OLED pixels and arrays were fabricated on a polymeric substrate. Displays fabricated on a polymeric substrates would be lightweight; flexible, more rugged, and potentially less expensive to fabricate. Many of the difficulties associated with fabricating active-matrix backplanes on flexible substrates were studied and addressed.

Performance evaluation soil samples utilizing encapsulation technology

DOEpatents

Dahlgran, J.R.

1999-08-17

Performance evaluation soil samples and method of their preparation uses encapsulation technology to encapsulate analytes which are introduced into a soil matrix for analysis and evaluation by analytical laboratories. Target analytes are mixed in an appropriate solvent at predetermined concentrations. The mixture is emulsified in a solution of polymeric film forming material. The emulsified solution is polymerized to form microcapsules. The microcapsules are recovered, quantitated and introduced into a soil matrix in a predetermined ratio to form soil samples with the desired analyte concentration. 1 fig.

Performance evaluation soil samples utilizing encapsulation technology

DOEpatents

Dahlgran, James R.

1999-01-01

Performance evaluation soil samples and method of their preparation using encapsulation technology to encapsulate analytes which are introduced into a soil matrix for analysis and evaluation by analytical laboratories. Target analytes are mixed in an appropriate solvent at predetermined concentrations. The mixture is emulsified in a solution of polymeric film forming material. The emulsified solution is polymerized to form microcapsules. The microcapsules are recovered, quantitated and introduced into a soil matrix in a predetermined ratio to form soil samples with the desired analyte concentration.

Synthesis of Size-Tunable CO2-Philic Imprinted Polymeric Particles (MIPs) for Low-Pressure CO2 Capture Using Oil-in-Oil Suspension Polymerization.

PubMed

Nabavi, Seyed Ali; Vladisavljević, Goran T; Zhu, Yidi; Manović, Vasilije

2017-10-03

Highly selective molecularly imprinted poly[acrylamide-co-(ethylene glycol dimethacrylate)] polymer particles (MIPs) for CO 2 capture were synthesized by suspension polymerization via oil-in-oil emulsion. Creation of CO 2 -philic, amide-decorated cavities in the polymer matrix led to a high affinity to CO 2 . At 0.15 bar CO 2 partial pressure, the CO 2 /N 2 selectivity was 49 (corresponding to 91% purity of the gas stream after regeneration), and reached 97 at ultralow CO 2 partial pressures. The imprinted polymers showed considerably higher CO 2 uptakes compared to their nonimprinted counterparts, and the maximum equilibrium CO 2 capture capacity of 1.1 mmol g -1 was achieved at 273 K. The heat of adsorption was below 32 kJ mol -1 and the temperature of onset of intense thermal degradation was 351-376 °C. An increase in monomer-to-cross-linker molar ratio in the dispersed phase up to 1:2.5 led to a higher affinity toward CO 2 due to higher density of selective amide groups in the polymer network. MIPs are a promising option for industrial packed and fluidized bed CO 2 capture systems due to large particles with a diameter up to 1200 μm and irregular oblong shapes formed due to arrested coalescence during polymerization, occurring as a result of internal elasticity of the partially polymerized semisolid drops.

Low toxicity high temperature PMR polyimide

NASA Technical Reports Server (NTRS)

Pater, Ruth H. (Inventor)

1992-01-01

In-situ polymerization of monomer reactants (PMR) type polyimides constitute an important class of ultra high performance composite matrix resins. PMR-15 is the best known and most widely used PMR polyimide. An object of the present invention is to provide a substantially improved high temperature PMR-15 system that exhibits better processability, toughness, and thermo-oxidative stability than PMR-15, as well as having a low toxicity. Another object is to provide new PMR polyimides that are useful as adhesives, moldings, and composite matrices. By the present invention, a new PMR polyimide comprises a mixture of the following compounds: 3,4'-oxydianiline (3,4'-ODA), NE, and BTDE which are then treated with heat. This PMR was designated LaRC-RP46 and has a broader processing window, better reproducibility of high quality composite parts, better elevated temperature mechanical properties, and higher retention of mechanical properties at an elevated temperature, particularly, at 371 C.

Radiation-induced polymerization of glass-forming systems. V. Initial polymerization rate in binary glass-forming systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaetsu, Isao; Okubo, Hiroshi; Ito, Akihiko

1973-06-01

The radiation-induced polymerization of binary systems consisting of glass-forming monomer and glass-forming solvent in supercooled phase was studied. The initial polymerization rates were markedly affected by T/sub g/ (glass transition temperature) and T/sub v/ of the system (30-50 deg C higher than T/sub g/), which are functions of the composition. The composition and temperature dependence of initial polymerization rate in binary glass-forming systems were much affected by homogeneity of the polymerization system and the T of the glass- forming solvent. The composition and temperature dependences in the glycidyl methacrylate --triacetin system as a typical homogeneous polymerization system were studied inmore » detail, and the polymerizations of hydroxyethyl methacrylate triacetln and hydroxyethyl methacrylate --isoamyl acetate systems were studied for the heterogeneous polymerization systems; the former illustrates the combination of lower T/sub g/ monomer and higher T/sub g/ solvent and the latter typifies a system consisting of higher T/sub g/ monomer and lower T/sub g/ solvent. All experimental results for the composition and temperature dependence of initial polymerization rate in binary glass-forming systems could be explained by considering the product of the effect of the physical effect relating to T/sub v/ and T/sub g/ of the system and the effect of composition in normal solution polymerization at higher temperature, which was also the product of a dilution effect and a chemical or physical acceleration effect. (auth)« less

Direct Preparation of Few Layer Graphene Epoxy Nanocomposites from Untreated Flake Graphite.

PubMed

Throckmorton, James; Palmese, Giuseppe

2015-07-15

The natural availability of flake graphite and the exceptional properties of graphene and graphene-polymer composites create a demand for simple, cost-effective, and scalable methods for top-down graphite exfoliation. This work presents a novel method of few layer graphite nanocomposite preparation directly from untreated flake graphite using a room temperature ionic liquid and laminar shear processing regimen. The ionic liquid serves both as a solvent and initiator for epoxy polymerization and is incorporated chemically into the matrix. This nanocomposite shows low electrical percolation (0.005 v/v) and low thickness (1-3 layers) graphite/graphene flakes by TEM. Additionally, the effect of processing conditions by rheometry and comparison with solvent-free conditions reveal the interactions between processing and matrix properties and provide insight into the theory of the chemical and physical exfoliation of graphite crystals and the resulting polymer matrix dispersion. An interaction model that correlates the interlayer shear physics of graphite flakes and processing parameters is proposed and tested.

Processing and Properties of Fiber Reinforced Polymeric Matrix Composites. Part 2; Processing Robustness of IM7/PETI Polyimide Composites

NASA Technical Reports Server (NTRS)

Hou, Tan-Hung

1996-01-01

The processability of a phenylethynyl terminated imide (PETI) resin matrix composite was investigated. Unidirectional prepregs were made by coating an N-methylpyrrolidone solution of the amide acid oligomer onto unsized IM7. Two batches of prepregs were used: one was made by NASA in-house, and the other was from an industrial source. The composite processing robustness was investigated with respect to the effect of B-staging conditions, the prepreg shelf life, and the optimal processing window. Rheological measurements indicated that PETI's processability was only slightly affected over a wide range of B-staging temperatures (from 250 C to 300 C). The open hole compression (OHC) strength values were statistically indistinguishable among specimens consolidated using various B-staging conditions. Prepreg rheology and OHC strengths were also found not to be affected by prolonged (i.e., up to 60 days) ambient storage. An optimal processing window was established using response surface methodology. It was found that IM7/PETI composite is more sensitive to the consolidation temperature than to the consolidation pressure. A good consolidation was achievable at 371 C/100 Psi, which yielded an OHC strength of 62 Ksi at room temperature. However, processability declined dramatically at temperatures below 350 C.

Tuning three-dimensional collagen matrix stiffness independently of collagen concentration modulates endothelial cell behavior.

PubMed

Mason, Brooke N; Starchenko, Alina; Williams, Rebecca M; Bonassar, Lawrence J; Reinhart-King, Cynthia A

2013-01-01

Numerous studies have described the effects of matrix stiffening on cell behavior using two-dimensional synthetic surfaces; however, less is known about the effects of matrix stiffening on cells embedded in three-dimensional in vivo-like matrices. A primary limitation in investigating the effects of matrix stiffness in three dimensions is the lack of materials that can be tuned to control stiffness independently of matrix density. Here, we use collagen-based scaffolds where the mechanical properties are tuned using non-enzymatic glycation of the collagen in solution, prior to polymerization. Collagen solutions glycated prior to polymerization result in collagen gels with a threefold increase in compressive modulus without significant changes to the collagen architecture. Using these scaffolds, we show that endothelial cell spreading increases with matrix stiffness, as does the number and length of angiogenic sprouts and the overall spheroid outgrowth. Differences in sprout length are maintained even when the receptor for advanced glycation end products is inhibited. Our results demonstrate the ability to de-couple matrix stiffness from matrix density and structure in collagen gels, and that increased matrix stiffness results in increased sprouting and outgrowth. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Creation of biological module for self-regulating ecological system by the way of polymerization of composite materials in free space.

PubMed

Kondyurin, A; Lauke, B; Kondyurina, I; Orba, E

2004-01-01

The large-size frame of space ship and space station can be created with the use of the technology of the polymerization of fiber-filled composites and a liquid reactionable matrix applied in free space or on the other space body when the space ship or space station will be used during a long period of time. For the polymerization of the station frame the fabric impregnated with a long-life polymer matrix (prepreg) is prepared in terrestrial conditions and, after folding, can be shipped in a compact container to orbit and kept folded on board the station. In due time the prepreg is carried out into free space and unfolded. Then a reaction of matrix polymerization starts. After reaction of polymerization the durable frame is ready for exploitation. After that, the frame can be filled out with air, the apparatus and life support systems. The technology can be used for creation of biological frame as element of self regulating ecological system, and for creation of technological frame which can be used for a production of new materials on Earth orbit in microgravity conditions and on other space bodies (Mars, Moon, asteroids) for unique high price mineral extraction. Based on such technology a future space base on Earth orbit with volume of 10(6) m3 and a crew of 100 astronauts is considered. c2004 COSPAR. Published by Elsevier Ltd. All rights reserved.

Emission pattern of semi-volatile organic compounds from recycled styrenic polymers using headspace solid-phase microextraction gas chromatography-mass spectrometry.

PubMed

Vilaplana, Francisco; Martínez-Sanz, Marta; Ribes-Greus, Amparo; Karlsson, Sigbritt

2010-01-15

The emission of low molecular weight compounds from recycled high-impact polystyrene (HIPS) has been investigated using headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS). Four released target analytes (styrene, benzaldehyde, acetophenone, and 2-phenylpropanal) were selected for the optimisation of the HS-SPME sampling procedure, by analysing operating parameters such as type of SPME fibre (polarity and operating mechanism), particle size, extraction temperature and time. 26 different compounds were identified to be released at different temperatures from recycled HIPS, including residues of polymerisation, oxidated derivates of styrene, and additives. The type of SPME fibre employed in the sampling procedure affected the detection of emitted components. An adsorptive fibre such as carbowax/polydimethylsiloxane (CAR/PDMS fibre) offered good selectivity for both non-polar and polar volatile compounds at lower temperatures; higher temperatures result in interferences from less-volatile released compounds. An absorptive fibre as polydimethylsiloxane (PDMS) fibre is suitable for the detection of less-volatile non-polar molecules at higher temperatures. The nature and relative amount of the emitted compounds increased with higher exposure temperature and smaller polymeric particle size. HS-SPME proves to be a suitable technique for screening the emission of semi-volatile organic compounds (SVOCs) from polymeric materials; reliable quantification of the content of target analytes in recycled HIPS is however difficult due to the complex mass-transfer processes involved, matrix effects, and the difficulties in equilibrating the analytical system. 2009 Elsevier B.V. All rights reserved.

Kinetics and Mechanism of in situ Simultaneous Formation of Metal Nanoparticles in Stabilizing Polymer Matrix

NASA Astrophysics Data System (ADS)

Pomogailo, Anatolii D.; Dzhardimalieva, Gulzhian I.; Rozenberg, Aleksander S.; Muraviev, Dmitri N.

2003-12-01

The kinetic peculiarities of the thermal transformations of unsaturated metal carboxylates (transition metal acrylates and maleates as well as their cocrystallites) and properties of metal-polymer nanocomposites formed have been studied. The composition and structure of metal-containing precursors and the products of the thermolysis were identified by X-ray analysis, optical and electron microscopy, magnetic measurements, EXAFS, IR and mass spectroscopy. The thermal transformations of metal-containing monomers studied are the complex process including dehydration, solid phase polymerization, and thermolysis process which proceed at varied temperature ranges. At 200-300°C the rate of thermal decay can be described by first-order equations. The products of decompositions are nanometer-sized particles of metal or its oxides with a narrow size distribution (the mean particle diameter of 5-10nm) stabilized by the polymer matrix.

Superabsorbent biphasic system based on poly(lactic acid) and poly(acrylic acid)

NASA Astrophysics Data System (ADS)

Sartore, Luciana; Pandini, Stefano; Baldi, Francesco; Bignotti, Fabio

2016-05-01

In this research work, biocomposites based on crosslinked particles of poly(acrylic acid), commonly used as superabsorbent polymer (SAP), and poly-L-lactic acid (PLLA) were developed to elucidate the role of the filler (i.e., polymeric crosslinked particles) on the overall physico-mechanical behavior and to obtain superabsorbent thermoplastic products. Samples prepared by melt-blending of components in different ratios showed a biphasic system with a regular distribution of particles, with diameter ranging from 5 to 10 μm, within the PLLA polymeric matrix. The polymeric biphasic system, coded PLASA i.e. superabsorbent poly(lactic acid), showed excellent swelling properties, demonstrating that cross-linked particles retain their superabsorbent ability, as in their free counterparts, even if distributed in a thermoplastic polymeric matrix. The thermal characteristics of the biocomposites evidence enhanced thermal stability in comparison with neat PLLA and also mechanical properties are markedly modified by addition of crosslinked particles which induce regular stiffening effect. Furthermore, in aqueous environments the particles swell and are leached from PLLA matrix generating very high porosity. These new open-pore PLLA foams, produced in absence of organic solvents and chemical foaming agents, with good physico-mechanical properties appear very promising for several applications, for instance in tissue engineering for scaffold production.

Preparation, characterization, and surface conductivity of nanocomposites with hollow graphitic carbon nanospheres as fillers in polymethylmethacrylate matrix

NASA Astrophysics Data System (ADS)

Zhang, Cheng; Gao, Qingshan; Zhou, Bing; Bhargava, Gaurang

2017-08-01

Hollow graphitized carbon nanosphere (CNS) materials with inner diameter of 20 to 50 nm and shell thickness of 10 15 nm were synthesized from the polymerization of resorcinol (R) and formaldehyde (F) in the presence of a well-characterized iron polymeric complex (IPC). The CNS with unique nanostructures was used to fabricate CNS-polymer composites by dispersing CNS as fillers in the polymer matrix. Aggregation of CNS in polymer composites is usually a challenging issue. In this work, we employed in situ polymerization method and melt-mixing method to fabricate CNS-polymethylmethacrylate (PMMA) composites and compared their difference in terms of CNS dispersion in the composites and surface electrical conductivity. Four probes technique was utilized to measure the surface electrical conductivity of the CNS-PMMA composites. The measurements on four points and four silver painted lines on the thin film of CNS-PMMA composites were compared. The in situ polymerization method was found more efficient for better CNS dispersion in PMMA matrix and lower percolation conductivity threshold compared to the melt-mixing method. The enhanced electrical conductivity for CNS-PMMA composites may be attributed to the stronger covalent CNS-PMMA bonding between the surface functional groups and the MMA moieties.

Identifying metabolic pathways for production of extracellular polymeric substances by the diatom Fragilariopsis cylindrus inhabiting sea ice.

PubMed

Aslam, Shazia N; Strauss, Jan; Thomas, David N; Mock, Thomas; Underwood, Graham J C

2018-05-01

Diatoms are significant primary producers in sea ice, an ephemeral habitat with steep vertical gradients of temperature and salinity characterizing the ice matrix environment. To cope with the variable and challenging conditions, sea ice diatoms produce polysaccharide-rich extracellular polymeric substances (EPS) that play important roles in adhesion, cell protection, ligand binding and as organic carbon sources. Significant differences in EPS concentrations and chemical composition corresponding to temperature and salinity gradients were present in sea ice from the Weddell Sea and Eastern Antarctic regions of the Southern Ocean. To reconstruct the first metabolic pathway for EPS production in diatoms, we exposed Fragilariopsis cylindrus, a key bi-polar diatom species, to simulated sea ice formation. Transcriptome profiling under varying conditions of EPS production identified a significant number of genes and divergent alleles. Their complex differential expression patterns under simulated sea ice formation was aligned with physiological and biochemical properties of the cells, and with field measurements of sea ice EPS characteristics. Thus, the molecular complexity of the EPS pathway suggests metabolic plasticity in F. cylindrus is required to cope with the challenging conditions of the highly variable and extreme sea ice habitat.

Material Properties of Matrix Lipids Determine Conformation and Intermolecular Reactivity of a Diacetylenic Phosphatidylcholine in the Lipid Bilayer

PubMed Central

Puri, Anu; Jang, Hyunbum; Yavlovich, Amichai; Masood, M. Athar; Veenstra, Timothy D.; Luna, Carlos; Aranda-Espinoza, Helim; Nussinov, Ruth; Blumenthal, Robert

2011-01-01

Photopolymerizable phospholipid DC8,9PC (1,2-bis-(tricosa-10,12-diynoyl)-sn-glycero-3-phosphocholine) exhibits unique assembly characteristics in the lipid bilayer. Due to the presence of the diacetylene groups, DC8,9PC undergoes polymerization upon UV (254 nm) exposure and assumes chromogenic properties. DC8,9PC photopolymerization in a gel phase matrix lipid 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) monitored by UV-VIS absorption spectroscopy occurred within 2 minutes after UV treatment, whereas no spectral shifts were observed when DC8,9PC was incorporated in a liquid phase matrix 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC). Liquid chromatography-tandem mass spectrometry analysis showed a decrease in DC8,9PC monomer in both DPPC and POPC environments without any change in matrix lipids in UV-treated samples. Molecular Dynamics (MD) simulations of DPPC/DC8,9PC and POPC/DC8,9PC bilayers indicate that the DC8,9PC molecules adjust to the thickness of the matrix lipid bilayer. Furthermore, motions of DC8,9PC in the gel phase bilayer are more restricted than in the fluid bilayer. The restricted motional flexibility of DC8,9PC (in the gel phase) enables the reactive diacetylenes in individual molecules to align and undergo polymerization, whereas the unrestricted motions in the fluid bilayer restrict polymerization due to the lack of appropriate alignment of the DC8,9PC fatty acyl chains. Fluorescence microscopy data indicates homogenous distribution of the lipid probe 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine-N-lissamine rhodamine B sulfonyl ammonium salt (N-Rh-PE) in POPC/DC8,9PC monolayers, but domain formation in DPPC/DC8,9PC monolayers. These results show that the DC8,9PC molecules cluster and assume the preferred conformation in the gel phase matrix for UV-triggered polymerization reaction. PMID:22053903

Fabrication and Handling of 3D Scaffolds Based on Polymers and Decellularized Tissues.

PubMed

Shpichka, Anastasia; Koroleva, Anastasia; Kuznetsova, Daria; Dmitriev, Ruslan I; Timashev, Peter

2017-01-01

Polymeric, ceramic and hybrid material-based three-dimensional (3D) scaffold or matrix structures are important for successful tissue engineering. While the number of approaches utilizing the use of cell-based scaffold and matrix structures is constantly growing, it is essential to provide a framework of their typical preparation and evaluation for tissue engineering. This chapter describes the fabrication of 3D scaffolds using two-photon polymerization, decellularization and cell encapsulation methods and easy-to-use protocols allowing assessing the cell morphology, cytotoxicity and viability in these scaffolds.

Detection of biological molecules using chemical amplification and optical sensors

DOEpatents

Van Antwerp, William Peter; Mastrototaro, John Joseph

2001-01-01

Methods are provided for the determination of the concentration of biological levels of polyhydroxylated compounds, particularly glucose. The methods utilize an amplification system that is an analyte transducer immobilized in a polymeric matrix, where the system is implantable and biocompatible. Upon interrogation by an optical system, the amplification system produces a signal capable of detection external to the skin of the patient. Quantitation of the analyte of interest is achieved by measurement of the emitted signal. Specifically, the analyte transducer immobilized in a polymeric matrix can be a boronic acid moiety.

Structural materials for space applications

NASA Technical Reports Server (NTRS)

Tenney, Darrel R.

1989-01-01

The long-term performance of structural materials in the space environment is a key research activity within NASA. The primary concerns for materials in low Earth orbit (LEO) are atomic oxygen erosion and space debris impact. Atomic oxygen studies have included both laboratory exposures in atomic oxygen facilities and flight exposures using the Shuttle. Characterization of atomic oxygen interaction with materials has included surface recession rates, residual mechanical properties, optical property measurements, and surface analyses to establish chemical changes. The Long Duration Exposure Facility (LDEF) is scheduled to be retrieved in 1989 and is expected to provide a wealth of data on atomic oxygen erosion in space. Hypervelocity impact studies have been conducted to establish damage mechanisms and changes in mechanical properties. Samples from LDEF will be analyzed to determine the severity of space debris impact on coatings, films, and composites. Spacecraft placed in geosynchronous Earth orbit (GEO) will be subjected to high doses of ionizing radiation which for long term exposures will exceed the damage threshold of many polymeric materials. Radiation interaction with polymers can result in chain scission and/or cross-linking. The formation of low molecular weight products in the epoxy plasticize the matrix at elevated temperatures and embrittle the matrix at low temperatures. This affects both the matrix-dominated mechanical properties and the dimensional stability of the composite. Embrittlement of the matrix at low temperatures results in enhanced matrix microcracking during thermal cycling. Matrix microcracking changes the coefficient of thermal expansion (CTE) of composite laminates and produces permanent length changes. Residual stress calculations were performed to estimate the conditions necessary for microcrack development in unirradiated and irradiated composites. The effects of UV and electron exposure on the optical properties of transparent polymer films were also examined to establish the optimum chemical structure for good radiation resistance. Thoughts on approaches to establishing accelerated testing procedures are discussed.

Electrical transport and thermochromic properties of polyaniline/chitosan/Co3O4 ternary nano composite

NASA Astrophysics Data System (ADS)

V, Mini; Kamath, Archana; S, Raghu; Chapi, Sharanappa; H, Devendrappa

2015-06-01

A new Polyaniline/ chitosan/ Co3O4 (CPAESCO) ternary nanocomposite is prepared by in situ oxidation polymerization of aniline in the presence of (NH4)2S2O8, chitosan and Co3O4. The Structural, Thermal, Optical and Electrical features of Polyaniline (PANI), Polyaniline/ chitosan (CPANI) and CPAESCO were analyzed using FT-IR, TGA, UV-vis analysis and Impedance spectroscopy by varying temperature. The results show that the introduction of the Co3O4 nanoparticles into CPANI matrix enhanced its properties. Mott's parameters show 3D -VRH Type conduction in it.

Radiation-induced polymerization of glass forming systems. VI. Polymerization rate at higher conversion in binary systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaetsu, I.; Ito, A.; Hayashi, K.

1973-08-01

The effect of temperature and composition on the inflection point in the time-conversion curve and the saturated conversion was investigated in the gamma -radio-induced radical polymerization of binary systems consisting of a glass- forming monomer and a solvent. In the polymerization of completely homogeneous systems such as glycidyl methacrylate (GMA) -triacetin and hydroxyethyl methacrylate (HEMA) --propylene glycol systems, the time-conversion curve has an inflection point at polymerization temperatures between T/sub vm/(T/sub v/ of monomer system) and T/sub vp/ (T/sub v/ of polymer system). Such conversions at the inflection point changed monotonically between 0 and 100% in this temperature range. T/submore » v/ was found to be 30 to 50 deg C higher than T/sub g/ (glass transition temperature) and a monotonic function of composition (monomer -- polymer -- solvent). The acceleration effect continued to 100% conversion above T/sub vp/, and no acceleration effect was observed below T/sub vm/. The saturated conversion in homogeneous systems changed monotonically between 0 and 100% for polymerization temperatures between T/sub gm/ (T/sub g/ of monomer system) and T/sub gp/(T of polymer system). T/sub g/ was also a monotonic function of composition. No saturation in conversion was observed above T/sub gp/ , and no polymerization occurred below T/sub gm/. In the polymerization of completely heterogeneous systems such as HEMA-dioctyl phthalate, no acceleration effect was observed at any temperature and composition. The saturated conversion was 100% sbove T/sub g/ of pure HEMA, and no polymerization occurred below this temperature in this system. (auth)« less

Adhesive F-actin Waves: A Novel Integrin-Mediated Adhesion Complex Coupled to Ventral Actin Polymerization

PubMed Central

Case, Lindsay B.; Waterman, Clare M.

2011-01-01

At the leading lamellipodium of migrating cells, protrusion of an Arp2/3-nucleated actin network is coupled to formation of integrin-based adhesions, suggesting that Arp2/3-mediated actin polymerization and integrin-dependent adhesion may be mechanistically linked. Arp2/3 also mediates actin polymerization in structures distinct from the lamellipodium, in “ventral F-actin waves” that propagate as spots and wavefronts along the ventral plasma membrane. Here we show that integrins engage the extracellular matrix downstream of ventral F-actin waves in several mammalian cell lines as well as in primary mouse embryonic fibroblasts. These “adhesive F-actin waves” require a cycle of integrin engagement and disengagement to the extracellular matrix for their formation and propagation, and exhibit morphometry and a hierarchical assembly and disassembly mechanism distinct from other integrin-containing structures. After Arp2/3-mediated actin polymerization, zyxin and VASP are co-recruited to adhesive F-actin waves, followed by paxillin and vinculin, and finally talin and integrin. Adhesive F-actin waves thus represent a previously uncharacterized integrin-based adhesion complex associated with Arp2/3-mediated actin polymerization. PMID:22069459

Monitoring migration and transformation of nanomaterials in polymeric composites during accelerated aging

NASA Astrophysics Data System (ADS)

Vilar, G.; Fernández-Rosas, E.; Puntes, V.; Jamier, V.; Aubouy, L.; Vázquez-Campos, S.

2013-04-01

The incorporation of small amounts of nanoadditives in polymeric compounds can introduce new mechanical, physical, electrical, magnetic, thermal and/or optical properties. The properties of these advanced materials have enabled new applications in several industrial sectors (electronics, automotive, textile...). In particular, for the nanomaterials (NM) described in this work, multi-walled carbon nanotubes (MWCNT) and silicon dioxide nanoparticles (SiO2 NP), the following properties have been described: MWCNT act as nucleating agents in thermoplastics, and change viscosity, affecting dispersion, orientation, and therefore mechanical, thermal, and electrical properties; and SiO2 NP act as flame retardant and display improved electrical and mechanical properties. The work described here is focused on the evaluation of the migration and transformation of NM included in polymer nanocomposites (NC) during accelerated climatic ageing. To this aim, we generated polyamide 6 (PA6) NC with different degree of compatibility between the NM and the polymeric matrix. These NC were submitted to accelerated aging conditions to simulate outdoor conditions (simulation of the use phase of the polymeric NC). The NC contain as nanofillers MWCNT and SiO2 NP with different surface properties to influence the compatibility with the polymeric matrix. The generated NC were evaluated by scanning electron microscopy (SEM), transmission electron microscopy (TEM) with Energy-dispersive X-ray spectroscopy (EDX), thermogravimetry (TGA) and differential scanning calorimetry (DSC) before and after the aging process, to monitor the compatibility of the NM with the matrix: dispersion within the matrix, migration during aging, and modification of the polymer properties. The dispersion of SiO2 NP in the NC depended on their compatibility with the matrix. However, independently of their compatibility with the matrix, SiO2 NP were aggregated at the end of the accelerated aging process. In addition, degradation of the matrix and migration of nanoparticles to the surface was observed as well in the different types of SiO2 NP aged NC. Oppositely, compatibilized MWCNT (MWCNTMB) decreased the degradation of the polymer. Nevertheless, the nanomaterial migrated likewise to the surface during the ageing process. In order to evaluate the possible changes in the structure of nanomaterials due to the aging process, NM were extracted from the polymer by calcination. The nanomaterials extracted were analyzed by TGA, Fourier transform infrared spectroscopy (FT-IR), BET and TEM and its properties compared with calcinated raw NM. SiO2 hydrophilic nanoparticles were not affected by the aging process. However, both types of MWCNT were affected by the aging of the NC.

Do adhesive systems leave resin coats on the surfaces of the metal matrix bands? An adhesive remnant characterization.

PubMed

Arhun, Neslihan; Cehreli, Sevi Burcak

2013-01-01

Reestablishing proximal contacts with composite resins may prove challenging since the applied adhesives may lead to resin coating that produces additional thickness. The aim of this study was to investigate the surface of metal matrix bands after application of adhesive systems and blowing or wiping off the adhesive before polymerization. Seventeen groups of matrix bands were prepared. The remnant particles were characterized by energy dispersive spectrum and scanning electron microscopy. Total etch and two-step self-etch adhesives did not leave any resin residues by wiping and blowing off. All-in-one adhesive revealed resin residues despite wiping off. Prime and Bond NT did not leave any remnant with compomer. Clinicians must be made aware of the consequences of possible adhesive remnants on matrix bands that may lead to a defective definitive restoration. The adhesive resin used for Class II restorations may leave resin coats on metal matrix bands after polymerization, resulting in additional thickness on the metal matrix bands and poor quality of the proximal surface of the definitive restoration when the adhesive system is incorporated in the restoration.

A Versatile Click-Compatible Monolignol Probe to Study Lignin Deposition in Plant Cell Walls

PubMed Central

Pandey, Jyotsna L.; Wang, Bo; Diehl, Brett G.; Richard, Tom L.; Chen, Gong; Anderson, Charles T.

2015-01-01

Lignin plays important structural and functional roles in plants by forming a hydrophobic matrix in secondary cell walls that enhances mechanical strength and resists microbial decay. While the importance of the lignin matrix is well documented and the biosynthetic pathways for monolignols are known, the process by which lignin precursors or monolignols are transported and polymerized to form this matrix remains a subject of considerable debate. In this study, we have synthesized and tested an analog of coniferyl alcohol that has been modified to contain an ethynyl group at the C-3 position. This modification enables fluorescent tagging and imaging of this molecule after its incorporation into plant tissue by click chemistry-assisted covalent labeling with a fluorescent azide dye, and confers a distinct Raman signature that could be used for Raman imaging. We found that this monolignol analog is incorporated into in vitro-polymerized dehydrogenation polymer (DHP) lignin and into root epidermal cell walls of 4-day-old Arabidopsis seedlings. Incorporation of the analog in stem sections of 6-week-old Arabidopsis thaliana plants and labeling with an Alexa-594 azide dye revealed the precise locations of new lignin polymerization. Results from this study indicate that this molecule can provide high-resolution localization of lignification during plant cell wall maturation and lignin matrix assembly. PMID:25884205

Preparation of nano-structured polymeric proton conducting membranes for use in fuel cells.

PubMed

Alberti, Giulio; Casciola, Mario; Pica, Monica; Di Cesare, Giusi

2003-03-01

We briefly discuss the state of the art of polymer electrolyte membrane fuel cells and suggest that the main obstacles to the commercial development of these fuel cells are essentially the high costs and poor characteristics of present proton conducting membranes. A strategy for the preparation of improved nanocomposite membranes based on the introduction of proton conducting lamell? in the polymeric matrix of present ionomeric membranes is then discussed. Due to their high proton conductivity (in some cases even higher than 10(-1) S cm(-1)), tailor made lamellae obtained by exfoliation of superacid metal (IV) phosphonates are particularly suitable for the preparation of these hybrid membranes. The expected positive influence of the dispersed lamellae on important properties of proton conducting membranes, such as swelling, mechanical resistance, proton transport, and diffusion of methanol, are also discussed. The methods used to obtain good lamellar dispersions into ionomeric polymers and the preparation and main characteristics of some hybrid membranes are also briefly described. The presence of nanoparticles of metal phosphonates in the electrodic interfaces Nafion/Pt already considerably improves the electrochemical characteristics of fuel cells in the temperature range 80-130 degrees C. The increased working temperature of the fuel cell considerably reduces CO poisoning of the platinum electrodes and allows better control of the cooling system, thus overcoming important obstacles to the development of medium temperature PEM fuel cells.

Simultaneous acoustic and dielectric real time curing monitoring of epoxy systems

NASA Astrophysics Data System (ADS)

Gkikas, G.; Saganas, Ch.; Grammatikos, S. A.; Aggelis, D. G.; Paipetis, A. S.

2012-04-01

The attainment of structural integrity of the reinforcing matrix in composite materials is of primary importance for the final properties of the composite structure. The detailed monitoring of the curing process on the other hand is paramount (i) in defining the optimal conditions for the impregnation of the reinforcement by the matrix (ii) in limiting the effects of the exotherm produced by the polymerization reaction which create unwanted thermal stresses and (iii) in securing optimal behavior in matrix controlled properties, such as off axis or shear properties and in general the durability of the composite. Dielectric curing monitoring is a well known technique for distinguishing between the different stages of the polymerization of a typical epoxy system. The technique successfully predicts the gelation and the vitrification of the epoxy and has been extended for the monitoring of prepregs. Recent work has shown that distinct changes in the properties of the propagated sound in the epoxy which undergoes polymerization is as well directly related to the gelation and vitrification of the resin, as well as to the attainment of the final properties of the resin system. In this work, a typical epoxy is simultaneously monitored using acoustic and dielectric methods. The system is isothermally cured in an oven to avoid effects from the polymerization exotherm. Typical broadband sensors are employed for the acoustic monitoring, while flat interdigital sensors are employed for the dielectric scans. All stages of the polymerization process were successfully monitored and the validity of both methods was cross checked and verified.

Polyhedral oligomeric silsesquioxane grafted polymer in polymeric foam

DOEpatents

King, Bruce A.; Patankar, Kshitish A.; Costeux, Stephane; Jeon, Hyun K.

2017-01-17

A polymeric foam article with a polymer matrix defining multiple cells therein has a polymer component with a first polymer that is a polyhedral oligomeric silsesquioxane grafted polymer that has a weight-average molecular weight of two kilograms per mole or higher and 200 kilograms per mole or lower.

Integration of CuAAC Polymerization and Controlled Radical Polymerization into Electron Transfer Mediated "Click-Radical" Concurrent Polymerization.

PubMed

Xue, Wentao; Wang, Jie; Wen, Ming; Chen, Gaojian; Zhang, Weidong

2017-03-01

The successful chain-growth copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) polymerization employing Cu(0)/pentamethyldiethylenetriamine (PMDETA) and alkyl halide as catalyst is first investigated by a combination of nuclear magnetic resonance, gel-permeation chromatography, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. In addition, the electron transfer mediated "click-radical" concurrent polymerization utilizing Cu(0)/PMDETA as catalyst is successfully employed to generate well-defined copolymers, where controlled CuAAC polymerization of clickable ester monomer is progressed in the main chain acting as the polymer backbone, the controlled radical polymerization (CRP) of acrylic monomer is carried out in the side chain. Furthermore, it is found that there is strong collaborative effect and compatibility between CRP and CuAAC polymerization to improve the controllability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis of the thermal reaction products of para polyphenylene by combined gas chromatography-mass spectrometry

NASA Technical Reports Server (NTRS)

Fewell, L. L.

1976-01-01

Analysis of the volatiles and sublimate produced when para-polyphenylene is pyrolyzed to constant weight under vacuum in the temperature range from 380 to 1000 C indicates that the polymer undergoes thermal degradation in two stages. The first stage involved dehydrohalogenation, which is essentially a curing reaction that produces crosslinking between polyphenylene chains resulting from the loss of chlorine from the polymer in the form of hydrogen chloride. The second stage of the thermal degradation is dehydrogenation because hydrogen is the major volatile species. Increasing amounts of polycyclic aromatic hydrocarbons (phenanthrene and 9, 10 benzphenanthrene) in the sublimate, concomitant with increasing C/H ratios of the polymeric residue with pyrolysis temperature, is consistent with the buildup of polynuclear structures in the polymer matrix.

Omega-3 PUFA concentration by a novel PVDF nano-composite membrane filled with nano-porous silica particles.

PubMed

Ghasemian, Samaneh; Sahari, Mohammad Ali; Barzegar, Mohsen; Ahmadi Gavlighi, Hasan

2017-09-01

In this study, polyvinylidene fluoride (PVDF) and nano-porous silica particle were used to fabricate an asymmetric nano-composite membrane. Silica particles enhanced the thermal stability of PVDF/SiO 2 membranes; increasing the decomposition temperature from 371°C to 408°C. Cross sectional morphology showed that silica particles were dispersed in polymer matrix uniformly. However, particle agglomeration was found at higher loading of silica (i.e., 20 by weight%). The separation performance of nano-composite membranes was also evaluated using the omega-3 polyunsaturated fatty acids (PUFA) concentration at a temperature and pressure of 30°C and 4bar, respectively. Silica particle increased the omega-3PUFA concentration from 34.8 by weight% in neat PVDF to 53.9 by weight% in PVDF with 15 by weight% of silica. Moreover, PVDF/SiO 2 nano-composite membranes exhibited enhanced anti-fouling property compared to neat PVDF membrane. Fouling mechanism analysis revealed that complete pore blocking was the predominant mechanism occurring in oil filtration. The concentration of omega-3 polyunsaturated fatty acids (PUFA) is important in the oil industries. While the current methods demand high energy consumptions in concentrating the omega-3, membrane separation technology offers noticeable advantages in producing pure omega-3 PUFA. Moreover, concentrating omega-3 via membrane separation produces products in the triacylglycerol form which possess better oxidative stability. In this work, the detailed mechanisms of fouling which limits the performance of membrane separation were investigated. Incorporating silica particles to polymeric membrane resulted in the formation of mixed matrix membrane with improved anti-fouling behaviour compared to the neat polymeric membrane. Hence, the industrial potential of membrane processing to concentrate omega-3 fatty acids is enhanced. Copyright © 2017. Published by Elsevier Ltd.

Melting line of polymeric nitrogen

NASA Astrophysics Data System (ADS)

Yakub, L. N.

2013-05-01

We made an attempt to predict location of the melting line of polymeric nitrogen using two equations for Helmholtz free energy: proposed earlier for cubic gauche-structure and developed recently for liquid polymerized nitrogen. The P-T relation, orthobaric densities and latent heat of melting were determined using a standard double tangent construction. The estimated melting temperature decreases with increasing pressure, alike the temperature of molecular-nonmolecular transition in solid. We discuss the possibility of a triple point (solid-molecular fluid-polymeric fluid) at ˜80 GPa and observed maximum of melting temperature of nitrogen.

Cost-efficient entrapment of β-glucosidase in nanoscale latex and silicone polymeric thin films for use as stable biocatalysts.

PubMed

Javed, Muhammad Rizwan; Buthe, Andreas; Rashid, Muhammad Hamid; Wang, Ping

2016-01-01

β-Glucosidase is an ubiquitous enzyme which has enormous biotechnological applications. Its deficiency in natural enzyme preparations is often overcome by exogenous supplementation, which further increases the enzyme utilization cost. Enzyme immobilization offers a potential solution through enzyme recycling and easy recovery. In the present work Aspergillus niger β-glucosidase is immobilized within nanoscale polymeric materials (polyurethane, latex and silicone), through entrapment, and subsequently coated onto a fibrous support. Highest apparent activity (90 U g(-1) polymer) was observed with latex, while highest entrapment efficiency (93%) was observed for the silicone matrix. Immobilization resulted in the thermo-stabilization of the β-glucosidase with an increase in optimum temperature and activation energy for cellobiose hydrolysis. Supplementation to cellulases also resulted in an increased cellulose hydrolysis, while retaining more than 70% functional stability. Hence, the current study describes novel preparations of immobilized β-glucosidase as highly stable and active catalysts for industrial food- and bio-processing applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Depth of cure of proximal composite resin restorations using a new perforated metal matrix.

PubMed

Nguyen, Duke P; Motyka, Nancy C; Meyers, Erik J; Vandewalle, Kraig S

2018-01-01

The purpose of this study was to compare the depths of cure of a proximal box preparation filled in bulk with various approaches: filled with a bulk-fill or conventional composite; placed with a new perforated metal matrix, a traditional metal matrix, or a clear matrix; and polymerized with either occlusal-only or tri-sited light curing. After tri-sited curing, the use of the new perforated metal matrix band resulted in a depth of cure that was not significantly different from that achieved with the use of metal bands (removed during curing) or transparent matrix bands. Adequate polymerization was obtained at depths of more than 5.0 mm for the bulk-fill composite and more than 4.0 mm for the conventional composite when tri-sited light curing was used. Tri-sited light curing resulted in a significantly greater depth of cure than occlusal-only curing. The perforated metal band may be used as an alternative to the use of solid metal bands or transparent matrix bands to provide similar depths of cure for composite resins, with the possible benefits of malleability and the ability to leave the band in place during tri-sited light curing.

Preceramic Polymers for Use as Fiber Coatings

NASA Technical Reports Server (NTRS)

Heimann, P. J.; Hurwitz, F. I.; Wheeler, D.; Eldridge, J.; Baranwal, R.; Dickerson, R.

1996-01-01

Polymeric precursors to Si-C-O, SI-B-N and Si-C were evaluated for use as ceramic interfaces in ceramic matrix composites. Use of the preceramic polymers allows for easy dip coating of fibers from dilute solutions of a polymer, which are then pyrolyzed to obtain the ceramic. SCS-0 fibers (Textron Specialty Materials, Lowell, MA) were coated with polymers from three systems: polysilsesquioxanes, polyborosilazanes and polycarbosilanes. The polysilsesquioxane systems were shown to produce either silicon oxycarbide or silicon oxynitride, depending on the pyrolysis conditions, and demonstrated some promise in an RBSN (reaction-bonded silicon nitride) matrix model system. Polyborosilazanes were shown, in studies of bulk polymers, to give rise to oxidation resistant Si-B-N ceramics which remain amorphous to temperatures of 1600 C, and should therefore provide a low modulus interface. Polycarbosilanes produce amorphous carbon-rich Si-C materials which have demonstrated oxidation resistance.

Polymer Nanocomposites—A Comparison between Carbon Nanotubes, Graphene, and Clay as Nanofillers

PubMed Central

Bhattacharya, Mrinal

2016-01-01

Nanofilled polymeric matrices have demonstrated remarkable mechanical, electrical, and thermal properties. In this article we review the processing of carbon nanotube, graphene, and clay montmorillonite platelet as potential nanofillers to form nanocomposites. The various functionalization techniques of modifying the nanofillers to enable interaction with polymers are summarized. The importance of filler dispersion in the polymeric matrix is highlighted. Finally, the challenges and future outlook for nanofilled polymeric composites are presented. PMID:28773388

Thermo- and pH-responsive polymer brushes-grafted gigaporous polystyrene microspheres as a high-speed protein chromatography matrix.

PubMed

Qu, Jian-Bo; Xu, Yu-Liang; Liu, Jun-Yi; Zeng, Jing-Bin; Chen, Yan-Li; Zhou, Wei-Qing; Liu, Jian-Guo

2016-04-08

Dual thermo- and pH-responsive chromatography has been proposed using poly(N-isopropylacrylamide-co-butyl methacrylate-co-N,N-dimethylaminopropyl acrylamide) (P(NIPAM-co-BMA-co-DMAPAAM)) brushes grafted gigaporous polystyrene microspheres (GPM) as matrix. Atom transfer radical polymerization (ATRP) initiator was first coupled onto GPM through Friedel-Crafts acylation with 2-bromoisobutyryl bromide. The dual-responsive polymer brushes were then grafted onto GPM via surface-initiated ATRP. The surface composition, gigaporous structure, protein adsorption and dual-responsive chromatographic properties of the matrix (GPM-P(NIPAM-co-BMA-co-DMAPAAM) were characterized in detail. Results showed that GPM were successfully grafted with thermoresponsive cationic polymer brushes and that the gigaporous structure was well maintained. A column packed with GPM-P(NIPAM-co-BMA-co-DMAPAAM presented low backpressure, good permeability and appreciable thermo-responsibility. By changing pH of the mobile phase and temperature of the column in turn, the column can separate three model proteins at the mobile phase velocity up to 2528cmh(-1). A separation mechanism of this matrix was also proposed. All results indicate that the dual thermo- and pH-responsive chromatography matrix has great potentials in 'green' high-speed protein chromatography. Copyright © 2016 Elsevier B.V. All rights reserved.

Multifunctional and biologically active matrices from multicomponent polymeric solutions

NASA Technical Reports Server (NTRS)

Kiick, Kristi L. (Inventor); Yamaguchi, Nori (Inventor); Rabolt, John (Inventor); Casper, Cheryl (Inventor)

2012-01-01

A functionalized electrospun matrix for the controlled-release of biologically active agents, such as growth factors, is presented. The functionalized matrix comprises a matrix polymer, a compatibilizing polymer and a biomolecule or other small functioning molecule. In certain aspects the electrospun polymer fibers comprise at least one biologically active molecule functionalized with low molecular weight heparin.

Self-Healing Laminate System

NASA Technical Reports Server (NTRS)

Keller, Michael W. (Inventor); White, Scott R. (Inventor); Beiermann, Brett A. (Inventor); Sottos, Nancy R. (Inventor)

2016-01-01

A laminate material may include a first flexible layer, and a self-healing composite layer in contact with the first flexible layer. The composite layer includes an elastomer matrix, a plurality of first capsules including a polymerizer, and a corresponding activator for the polymerizer. The laminate material may self-heal when subjected to a puncture or a tear.

Stress reduction in phase-separated, cross-linked networks: influence of phase structure and kinetics of reaction

PubMed Central

Szczepanski, Caroline R.; Stansbury, Jeffrey W.

2014-01-01

A mechanism for polymerization shrinkage and stress reduction was developed for heterogeneous networks formed via ambient, photo-initiated polymerization-induced phase separation (PIPS). The material system used consists of a bulk homopolymer matrix of triethylene glycol dimethacrylate (TEGDMA) modified with one of three non-reactive, linear prepolymers (poly-methyl, ethyl and butyl methacrylate). At higher prepolymer loading levels (10–20 wt%) an enhanced reduction in both shrinkage and polymerization stress is observed. The onset of gelation in these materials is delayed to a higher degree of methacrylate conversion (~15–25%), providing more time for phase structure evolution by thermodynamically driven monomer diffusion between immiscible phases prior to network macro-gelation. The resulting phase structure was probed by introducing a fluorescently tagged prepolymer into the matrix. The phase structure evolves from a dispersion of prepolymer at low loading levels to a fully co-continuous heterogeneous network at higher loadings. The bulk modulus in phase separated networks is equivalent or greater than that of poly(TEGDMA), despite a reduced polymerization rate and cross-link density in the prepolymer-rich domains. PMID:25418999

Self-Propagating Frontal Polymerization in Water at Ambient Pressure

NASA Technical Reports Server (NTRS)

Olten, Nesrin; Kraigsley, Alison; Ronney, Paul D.

2003-01-01

Advances in polymer chemistry have led to the development of monomers and initiation agents that enable propagating free-radical polymerization fronts to exist. These fronts are driven by the exothermicity of the polymerization reaction and the transport of heat from the polymerized product to the reactant monomer/solvent/initiator solution. The thermal energy transported to the reactant solution causes the initiator to decompose, yielding free radicals, which start the free radical polymerization process as discussed in recent reviews. The use of polymerization processes based on propagating fronts has numerous applications. Perhaps the most important of these is that it enables rapid curing of polymers without external heating since the polymerization process itself provides the high temperatures necessary to initiate and sustain polymerization. This process also enables more uniform curing of arbitrarily thick samples since it does not rely on heat transfer from an external source, which will necessarily cause the temperature history of the sample to vary with distance from the surface according to a diffusion-like process. Frontal polymerization also enables filling and sealing of structures having cavities of arbitrary shape without having to externally heat the structure. Water at atmospheric pressure is most convenient solvent to employ and the most important for practical applications (because of the cost and environmental issues associated with DMSO and other solvents). Nevertheless, to our knowledge, steady, self-propagating polymerization fronts have not been reported in water at atmospheric pressure. Currently, polymerization fronts require a high boiling point solvent (either water at high pressures or an alternative solvent such as dimethyl sulfoxide (DMSO) (boiling point 189 C at atmospheric pressure.) Early work on frontal polymerization, employed pressures up to 5000 atm in order to avoid boiling of the monomer/solvent/initiator solution. High boiling point solutions are needed because in order to produce a propagating front, a high front temperature is needed to produce sufficiently rapid decomposition of the free radical initiator and subsequent free radical polymerization and heat release at a rate faster than heat losses remove thermal energy from the system. (While the conduction heat loss rate increases linearly with temperature, the free radical initiator decomposition is a high activation energy process whose rate increases much more rapidly than linearly with temperature, thus as the temperature decreases, the ratio of heat loss to heat generation increases, eventually leading to extinction of the front if the temperature is too low.) In order to obtain atmospheric pressure frontal polymerization in water, it is necessary to identify a monomer/initiator combination that is water soluble and will not extinguish even when the peak temperature (T*) is less than 100 C. In this work acrylic acid (AA) was chosen as the monomer because is it one of the most reactive monomers and can polymerize readily at low temperatures even without initiators. Ammonium persulfate (AP) was chosen as the initiator because it decomposes readily at low temperatures, produces relatively few bubbles and is commercially available. The propagation rates and extinction conditions of the fronts are studied for a range of AA and AP concentrations. Small amounts of fumed silica powder (Cab-o-sil, Cabot Corporation) were added to the solutions to inhibit buoyancy induced convection in the solutions; future studies will investigate the effects of buoyant convection within the solutions.

Study of aniline polymerization reactions through the particle size formation in acidic and neutral medium

NASA Astrophysics Data System (ADS)

Aribowo, Slamet; Hafizah, Mas Ayu Elita; Manaf, Azwar; Andreas

2018-04-01

In the present paper, we reported particle size kinetic studies on the conducting polyaniline (PANI) which synthesized through a chemical oxidative polymerization technique from aniline monomer. PANI was prepared using ammonium persulfate (APS) as oxidizing agent which carried out in acidic and neutral medium at various batch temperatures of respectively 20, 30 and 50 °C. From the studies, it was noticed that the complete polymerization reaction progressed within 480 minutes duration time. The pH of the solution during reaction kinetic reached values 0.8 - to 1.2 in acidic media, while in the neutral media the pH value reached values 3.8 - 4.9. The batch temperature controlled the polymerization reaction in which the reaction progressing, which followed by the temperature rise of solution above the batch temperature before settled down to the initial temperature. An increment in the batch temperature gave highest rise in the solution temperature for the two media which cannot be more than 50 °C. The final product of polymerization reaction was PANI confirmed by Fourier Transform Infra-Red (FTIR) spectrophotometer for molecule structure identification. The averages particle size of PANI which carried out in the two different media is evidently similar in the range 30 - 40 μm and insensitive to the batch temperature. However, the particle size of PANI which obtained from the polymerization reaction at a batch temperature of 50 °C under acidic condition reached ˜53.1 μm at the tip of the propagation stage which started in the first 5 minutes. The size is obviously being the largest among the batch temperatures. Whereas, under neutral condition the particle size is much larger which reached the size 135 μm at the batch temperature of 20 °C. It is concluded that the particle size formation during the polymerization reaction being one of the important parameter to determine particle growing of polymer which indicated the reaction kinetics mechanism of synthesize polyaniline.

Polymeric dental composites based on remineralizing amorphous calcium phosphate fillers

PubMed Central

Skrtic, Drago; Antonucci, Joseph M.

2017-01-01

For over two decades we have systematically explored structure-composition-property relationships of amorphous calcium phosphate (ACP)-based polymeric dental composites. The appeal of these bioactive materials stems from their intrinsic ability to prevent demineralization and/or restore defective tooth structures via sustained release of remineralizing calcium and phosphate ions. Due to the compositional similarity of the ACP to biological tooth mineral, ACP-based composites should exhibit excellent biocompatibility. Research described in this article has already yielded remineralizing sealants and orthodontic adhesives as well as a prototype root canal sealer. Our work has also contributed to a better understanding on how polymer matrix structure and filler/matrix interactions affect the critical properties of these polymeric composites and their overall performance. The addition of antimicrobial compounds to the formulation of ACP composites could increase their medical and dental regenerative treatment applications, thereby benefiting an even greater number of patients. PMID:29599572

Laser Printing of PCL/Progesterone Tablets for Drug Delivery Applications in Hormone Cancer Therapy

NASA Astrophysics Data System (ADS)

Salmoria, G. V.; Klauss, P.; Kanis, L. A.

2017-09-01

In this study, polycaprolactone (PCL) and progesterone (PG) tablets were produced by selective laser sintering (SLS) using different particle sizes and laser energy. The sintered PCL/PG tablets presented uniform morphology, coalescence of particles and interconnected pores distributed in the polymeric matrix. The EDS analysis confirmed the presence of progesterone recrystallized on the surface of the porous PCL matrix. The crystallinity values for the PCL/PG tablets were lower than that for the pure PCL, suggesting the interaction of components at the molecular level. The PCL/PG tablets fabricated with small particles and high laser energy presented a higher value for the flexural modulus compared with the other specimens. The glass transition temperature (Tg) was -37 °C for the PCL/PG tablet with a high degree of sintering. The fatigue test showed that the PCL/PG blend tablets have high fatigue strength. The drug release mechanism of all tablets studied followed a zero-order kinetics, and drug release rates were dependent on sintering degree and, consequently, on matrix erosion, showing a potential application to controlled drug delivery in hormone cancer therapy.

Hydrolase stabilization via entanglement in poly(propylene sulfide) nanoparticles: stability towards reactive oxygen species.

PubMed

Allen, Brett L; Johnson, Jermaine D; Walker, Jeremy P

2012-07-27

In the advancement of green syntheses and sustainable reactions, enzymatic biocatalysis offers extremely high reaction rates and selectivity that goes far beyond the reach of chemical catalysts; however, these enzymes suffer from typical environmental constraints, e.g. operational temperature, pH and tolerance to oxidative environments. A common hydrolase enzyme, diisopropylfluorophosphatase (DFPase, EC 3.1.8.2), has demonstrated a pronounced efficacy for the hydrolysis of a variety of substrates for potential toxin remediation, but suffers from the aforementioned limitations. As a means to enhance DFPase's stability in oxidative environments, enzymatic covalent immobilization within the polymeric matrix of poly(propylene sulfide) (PPS) nanoparticles was performed. By modifying the enzyme's exposed lysine residues via thiolation, DFPase is utilized as a comonomer/crosslinker in a mild emulsion polymerization. The resultant polymeric polysulfide shell acts as a 'sacrificial barrier' by first oxidizing to polysulfoxides and polysulfones, rendering DFPase in an active state. DFPase-PPS nanoparticles thus retain activity upon exposure to as high as 50 parts per million (ppm) of hypochlorous acid (HOCl), while native DFPase is observed as inactive at 500 parts per billion (ppb). This trend is also confirmed by enzyme-generated (chloroperoxidase (CPO), EC 1.11.1.10) reactive oxygen species (ROS) including both HOCl (3 ppm) and ClO(2) (100 ppm).

Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates and Method Relating Thereto

NASA Technical Reports Server (NTRS)

Simpson, Joycelyn O. (Inventor); St.Claire, Terry L. (Inventor)

2002-01-01

A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared, This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers, acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors. in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches. adjustable fresnel lenses, speakers, tactile sensors, weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 100 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrates; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

Thermally Stable, Piezoelectric and Pyroelectric Polymeric Substrates

NASA Technical Reports Server (NTRS)

Simpson, Joycely O. (Inventor); St.Clair, Terry L. (Inventor)

1999-01-01

A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers. acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors, in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors. weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 1000 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium; applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

Method of Making Thermally Stable, Piezoelectric and Proelectric Polymeric Substrates

NASA Technical Reports Server (NTRS)

Simpson, Joycelyn O. (Inventor); St.Clair, Terry L. (Inventor)

1999-01-01

A thermally stable, piezoelectric and pyroelectric polymeric substrate was prepared. This thermally stable, piezoelectric and pyroelectric polymeric substrate may be used to prepare electromechanical transducers, thermomechanical transducers, accelerometers, acoustic sensors, infrared sensors, pressure sensors, vibration sensors, impact sensors. in-situ temperature sensors, in-situ stress/strain sensors, micro actuators, switches, adjustable fresnel lenses, speakers, tactile sensors, weather sensors, micro positioners, ultrasonic devices, power generators, tunable reflectors, microphones, and hydrophones. The process for preparing these polymeric substrates includes: providing a polymeric substrate having a softening temperature greater than 100 C; depositing a metal electrode material onto the polymer film; attaching a plurality of electrical leads to the metal electrode coated polymeric substrate; heating the metal electrode coated polymeric substrate in a low dielectric medium: applying a voltage to the heated metal electrode coated polymeric substrate to induce polarization; and cooling the polarized metal electrode coated polymeric electrode while maintaining a constant voltage.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir; Roghani-Mamaqani, Hossein

Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presencemore » of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric analysis shows that thermal stability of the nanocomposites increases by adding nanoparticles content. Decrease of glass transition temperature is also demonstrated by the addition of 3 wt% of silica nanoparticles according to the differential scanning calorimetry results.« less

Matrix-assisted laser desorption/ionization sample preparation optimization for structural characterization of poly(styrene-co-pentafluorostyrene) copolymers.

PubMed

Tisdale, Evgenia; Kennedy, Devin; Xu, Xiaodong; Wilkins, Charles

2014-01-15

The influence of the sample preparation parameters (the choice of the matrix, matrix:analyte ratio, salt:analyte ratio) was investigated and optimal conditions were established for the MALDI time-of-flight mass spectrometry analysis of the poly(styrene-co-pentafluorostyrene) copolymers. These were synthesized by atom transfer radical polymerization. Use of 2,5-dihydroxybenzoic acid as matrix resulted in spectra with consistently high ion yields for all matrix:analyte:salt ratios tested. The optimized MALDI procedure was successfully applied to the characterization of three copolymers obtained by varying the conditions of polymerization reaction. It was possible to establish the nature of the end groups, calculate molecular weight distributions, and determine the individual length distributions for styrene and pentafluorostyrene monomers, contained in the resulting copolymers. Based on the data obtained, it was concluded that individual styrene chain length distributions are more sensitive to the change in the composition of the catalyst (the addition of small amount of CuBr2) than is the pentafluorostyrene component distribution. Copyright © 2013 Elsevier B.V. All rights reserved.

Conductivity of gel polymer electrolytes doped with solutions of phosphonic acid or protic ionic liquids

NASA Astrophysics Data System (ADS)

Shmukler, Liudmila E.; Fadeeva, Yuliya A.; Glushenkova, Ekaterina V.; Nguyen, Van Thuc; Safonova, Liubov P.

2018-04-01

The proton-conducting gel electrolytes (PCGEs) based on PMMA, PVdF or PVdF-HFP doped with solutions of phosphonic acid or ammonium based protic ionic liquids (PILs) in DMF have been synthesized. Rather high values of the conductivity (10-4-10-3 S cm-1) have been reached at low dopant concentrations (up to 1 mol l-1). The influence of the nature of both polymeric matrix and dopant as well as dopant concentration on the conductivity values was discussed. It was established that the dependence of conductivity on the nature of dopant, but not the polymeric matrix, was more pronounced.

Multifunctional curing agents and their use in improving strength of composites containing carbon fibers embedded in a polymeric matrix

DOEpatents

Vautard, Frederic; Ozcan, Soydan

2017-04-11

A functionalized carbon fiber having covalently bound on its surface a sizing agent containing epoxy groups, at least some of which are engaged in covalent bonds with crosslinking molecules, wherein each of said crosslinking molecules possesses at least two epoxy-reactive groups and at least one free functional group reactive with functional groups of a polymer matrix in which the carbon fiber is to be incorporated, wherein at least a portion of said crosslinking molecules are engaged, via at least two of their epoxy-reactive groups, in crosslinking bonds between at least two epoxy groups of the sizing agent. Composites comprised of these functionalized carbon fibers embedded in a polymeric matrix are also described. Methods for producing the functionalized carbon fibers and composites thereof are also described.

Preparation and Characterization of Biomimetic Hydroxyapatite-Resorbable Polymer Composites for Hard Tissue Repair

NASA Astrophysics Data System (ADS)

Hiebner, Kristopher Robert

Autografts are the orthopedic "gold standard" for repairing bone voids. Autografts are osteoconductive and do not elicit an immune response, but they are in short supply and require a second surgery to harvest the bone graft. Allografts are currently the most common materials used for the repair of segmental defects in hard tissue. Unlike autografts, allografts can cause an undesirable immune response and the possibility of disease transmission is a major concern. As an alternative to the above approaches, recent research efforts have focused on the use of composite materials made from hydroxyapatite (HA) and bioresorbable polymers, such as poly-L-lactide (PLLA). Recent results have shown that the surface hydroxides on HA can initiate the ring opening polymerization (ROP) of L-lactide and other lactones creating a composite with superior interfacial strength. This thesis demonstrates that the surface of porous biologically derived HA substrates, such as coralline HA and trabecular bone, can be used to initiate the ROP of L-lactide and other lactones from the vapor phase. This process increases the strength of the porous scaffold through the deposition of a thin, uniform polymer coating, while maintaining the porous structure. The kinetics of the chemical vapor deposition polymerization (CVDP) are described using a quartz crystal microbalance (QCM). The reaction temperature and monomer vapor pressure are found to affect the rate of the polymerization. Also described in this thesis is the preparation of a porous polymer scaffold that mimics the structure of demineralized bone matrix (DBM). This demineralized bone matrix simulant (DBMS) is created using anorganic bovine bone as a template to initiate the polymerization of various lactones, followed by the removal of the HA scaffold. This material retained its shape and exhibits mechanical properties superior to DBM. Finally it is shown that HA can be used to initiate the ROP of a-caprolactam and the biocompatibility of various HA/bioresorbable polymer composites are described through the use of cell cultures run in collaboration with a research group specializing in immunology.

High-temperature resins

NASA Technical Reports Server (NTRS)

Serafini, T. T.

1982-01-01

The basic chemistry, cure processes, properties, and applications of high temperature resins known as polyimides are surveyed. Condensation aromatic polymides are prepared by reacting aromatic diamines with aromatic dianhydrides, aromatic tetracarboxylic acids, or with dialkyl esters of aromatic tetracarboxylic acids, depending on the intended end use. The first is for coatings or films while the latter two are more suitable for polyimide matrix resins. Prepreg solutions are made by dissolving reactants in an aprotic solvent, and advances in the addition of a diamine on the double bond and radical polymerization of the double bond are noted to have yielded a final cure product with void-free characteristics. Attention is given to properties of the Skybond, Pyralin, and NR-150B polyimide prepreg materials and characteristics of aging in the NP-150 polyimides. Finally, features of the NASA-developed PMR polyimides are reviewed.

Novel Precursor Approached for CMC Derived by Polymer Pyrolysis

DTIC Science & Technology

1994-02-15

to remove signals from probe polymer materials. C. Pyrolysis Methods The conversion of polymeric PMVS to SiC -containing ceramic was studied by... Composite Fabrication Methods Ceramic matrix composites with different matrix compositions were fabricated using the Polymer Impregnation- Pyrolysis (PIP...Pyrolyzed composites were re- infiltrated with the appropriate polymer matrix source under vacuum, and cured in an autoclave under 100 psi overpressure of N2

Polymerized laminin-332 matrix supports rapid and tight adhesion of keratinocytes, suppressing cell migration.

PubMed

Kariya, Yoshinobu; Sato, Hiroki; Katou, Naoko; Kariya, Yukiko; Miyazaki, Kaoru

2012-01-01

Laminin-332 (α3ß3γ2) (Lm332) supports the stable anchoring of basal keratinocytes to the epidermal basement membrane, while it functions as a motility factor for wound healing and cancer invasion. To understand these contrasting activities of Lm332, we investigated Lm332 matrices deposited by normal human keratinocytes and other Lm332-expressing cell lines. All types of the cells efficiently deposited Lm332 on the culture plates in specific patterns. On the contrary, laminins containing laminin ß1 and/or γ1 chains, such as Lm511 and Lm311, were not deposited on the culture plates even if secreted into culture medium. The Lm332 deposition was not inhibited by function-blocking antibodies to the α3 and α6 integrins but was inhibited by sodium selenate, suggesting that sulfated glycosaminoglycans on cell surface, e.g. heparan sulfate proteoglycans, might be involved in the process. HEK293 cells overexpressing exogenous Lm332 (Lm332-HEK) almost exclusively deposited Lm332 on the plates. The deposited Lm332 matrix showed a mesh-like network structure as analyzed by electron microscopy, suggesting that Lm332 was highly polymerized. When biological activity was analyzed, the Lm332 matrix rather suppressed the migration of keratinocytes as compared with purified Lm332, which highly promoted the cell migration. The Lm332 matrix supported adhesion of keratinocytes much more strongly and stably than purified Lm332. Integrin α3ß1 bound to the Lm332 matrix at a three times higher level than purified Lm332. Normal keratinocytes prominently showed integrin α6ß4-containing, hemidesmosome-like structures on the Lm332 matrix but not on the purified one. These results indicate that the polymerized Lm332 matrix supports stable cell adhesion by interacting with both integrin α6ß4 and α3ß1, whereas unassembled soluble Lm332 supports cell migration.

Polymeric Materials for Aerospace Power and Propulsion: Overview of Polymer Research at NASA Glenn

NASA Technical Reports Server (NTRS)

Meador, Michael A.

2007-01-01

Weight, durability and performance are all major concerns for any NASA mission. Use of lightweight materials, such as fiber reinforced polymer matrix composites can lead to significant reductions in vehicle weight and improvements in vehicle performance. Research in the Polymeric Materials Branch at NASA Glenn is focused on improving the durability, properties, processability and performance of polymeric materials by utilizing both conventional polymer science and engineering as well as nanotechnology and bioinspired approaches. This presentation will provide an overview of these efforts and highlight recent progress.

Functionalized ormosil scaffolds processed by direct laser polymerization for application in tissue engineering

NASA Astrophysics Data System (ADS)

Matei, A.; Schou, J.; Canulescu, S.; Zamfirescu, M.; Albu, C.; Mitu, B.; Buruiana, E. C.; Buruiana, T.; Mustaciosu, C.; Petcu, I.; Dinescu, M.

2013-08-01

Synthesized N,N'-(methacryloyloxyethyl triehtoxy silyl propyl carbamoyl-oxyhexyl)-urea hybrid methacrylate was polymerized by direct laser polymerization using femtosecond laser pulses with the aim of using it for subsequent applications in tissue engineering. The as-obtained scaffolds were modified either by low pressure argon plasma treatment or by covering the structures with two different proteins (lysozyme, fibrinogen). For improved adhesion, the proteins were deposited by matrix assisted pulsed laser evaporation technique. The functionalized structures were tested in mouse fibroblasts culture and the cells morphology, proliferation, and attachment were analyzed.

Transient inter-cellular polymeric linker.

PubMed

Ong, Siew-Min; He, Lijuan; Thuy Linh, Nguyen Thi; Tee, Yee-Han; Arooz, Talha; Tang, Guping; Tan, Choon-Hong; Yu, Hanry

2007-09-01

Three-dimensional (3D) tissue-engineered constructs with bio-mimicry cell-cell and cell-matrix interactions are useful in regenerative medicine. In cell-dense and matrix-poor tissues of the internal organs, cells support one another via cell-cell interactions, supplemented by small amount of the extra-cellular matrices (ECM) secreted by the cells. Here we connect HepG2 cells directly but transiently with inter-cellular polymeric linker to facilitate cell-cell interaction and aggregation. The linker consists of a non-toxic low molecular-weight polyethyleneimine (PEI) backbone conjugated with multiple hydrazide groups that can aggregate cells within 30 min by reacting with the aldehyde handles on the chemically modified cell-surface glycoproteins. The cells in the cellular aggregates proliferated; and maintained the cortical actin distribution of the 3D cell morphology while non-aggregated cells died over 7 days of suspension culture. The aggregates lost distinguishable cell-cell boundaries within 3 days; and the ECM fibers became visible around cells from day 3 onwards while the inter-cellular polymeric linker disappeared from the cell surfaces over time. The transient inter-cellular polymeric linker can be useful for forming 3D cellular and tissue constructs without bulk biomaterials or extensive network of engineered ECM for various applications.

Evaluation of the polymerization shrinkage of experimental flowable composite resins through optical coherence tomography

NASA Astrophysics Data System (ADS)

Carneiro, Vanda S. M.; Mota, Cláudia C. B. O.; Souza, Alex F.; Cajazeira, Marlus R. R.; Gerbi, Marleny E. M. M.; Gomes, Anderson S. L.

2018-02-01

This study evaluated the polymerization shrinkage of two experimental flowable composite resins (CR) with different proportions of Urethane dimethacrylate (UDMA)/triethylene glycol dimethacrylate (TEGDMA) monomers in the organic matrix (50:50 and 60:40, respectively). A commercially available flowable CR, Tetric N-Flow (Ivoclair Vivadent, Liechtenstein, Germany), was employed as the control group. The resins were inserted in a cylindrical teflon mold (7 mm diameter, 0.6 mm height) and scanned with OCT before photoactivation, immediately after and 15 minutes after light-curing (Radii-Cal, SDI, Australia, 1,200 mW/cm2 ) exposure. A Callisto SD-OCT system (Thorlabs Inc, USA), operating at 930 nm central wavelength was employed for imaging acquisition. Cross-sectional OCT images were captured with 8 mm transverse scanning (2000x512 matrix), and processed by the ImageJ software, for comparison between the scanning times and between groups. Pearson correlation showed significant shrinkage for all groups in each time analyzed. Kruskal-Wallis test showed greater polymerization shrinkage for the 50:50 UDMA/TEGDMA group (p=0.001), followed by the control group (p=0.018). TEGDMA concentration was proportionally related to the polymerization shrinkage of the flowable composite resins.

Preparation and characterization of a magneto-polymeric nanocomposite: Fe 3O 4 nanoparticles in a grafted, cross-linked and plasticized poly(vinyl chloride) matrix

NASA Astrophysics Data System (ADS)

Rodríguez-Fernández, Oliverio S.; Rodríguez-Calzadíaz, C. A.; Yáñez-Flores, Isaura G.; Montemayor, Sagrario M.

In this work two kind of materials: (1) grafted, cross-linked and plasticized poly(vinyl chloride) (PVC) "plastic films" and (2) magnetic plastic films "magneto-polymeric nanocomposites" were prepared. Precursor solutions or "plastisols" used to obtain the plastic films were obtained by mixing PVC (emulsion grade) as polymeric matrix, di(2-ethylhexyl)phthalate (DOP) as plasticizer, a thermal stabilizer based in Ca/Zn salts, and a cross-linking agent, 3-mercaptopropyltrimethoxysilane (MTMS) or 3-aminopropyltriethoxysilane (ATES), at several concentrations. Flexible films were obtained from the plastisols using static casting. The stress-strain behavior and the gel content (determined by Soxhlet extraction with boiling THF) of the flexible films were measured in order to evaluate the effect of the cross-linking agent and their content on the degree of cross-linking. The magneto-polymeric nanocomposites were obtained by mixing the optimum composition of the plastisols (analyzed previously) with magnetite (Fe 3O 4)-based ferrofluid and DOP. Later, flexible films were obtained by static casting of the plastisol/ferrofluid systems. The magnetic films were characterized by the above-mentioned techniques and X-ray diffraction, vibrating sample magnetometry and thermogravimetrical analysis.

Microwave Irradiation on Graphene Dispersed Within Polymeric Matrices

NASA Astrophysics Data System (ADS)

Cisneros, Jorge; Yust, Brian; Chipara, Mircea

Graphene is a two dimensional nanomaterial with high thermal and electric conductivity and Young modulus. These features make graphene an ideal reinforcement for polymeric matrices. However, the mechanical features of polymer-carbon nanostructured composites are limited by the dispersion of the filler and by the delamination or microcracks initiated at the interface between the polymeric matrix and nanofiller. This last weakness can be addressed by improving the interface via chemical and physical methods. Microwave heating of graphite is a very efficient approach if the polymeric matrix does not also have a strong absorption. During the irradiation, the nanofiller is preferentially heated; the local melting of the polymer at the interface improves the interface by filling the microcracks and delaminations. Nanocomposites of polystyrene-poly(ethylene-ran-butylene)-polystyrene loaded by various amounts of graphene ranging from 0 % to 20 % wt. have been prepared by solution mixing using chloroform as solvent. The as obtained nanocomposites have been subjected to microwave irradiation in an Anton Paar Monowave 300 system operating at 75 W, for various irradiation times 5, 10, 15, 30, 45, and 60 minutes. The effect of microwave irradiation has been studied by Raman spectroscopy.

In Situ Thermal Generation of Silver Nanoparticles in 3D Printed Polymeric Structures.

PubMed

Fantino, Erika; Chiappone, Annalisa; Calignano, Flaviana; Fontana, Marco; Pirri, Fabrizio; Roppolo, Ignazio

2016-07-19

Polymer nanocomposites have always attracted the interest of researchers and industry because of their potential combination of properties from both the nanofillers and the hosting matrix. Gathering nanomaterials and 3D printing could offer clear advantages and numerous new opportunities in several application fields. Embedding nanofillers in a polymeric matrix could improve the final material properties but usually the printing process gets more difficult. Considering this drawback, in this paper we propose a method to obtain polymer nanocomposites by in situ generation of nanoparticles after the printing process. 3D structures were fabricated through a Digital Light Processing (DLP) system by disolving metal salts in the starting liquid formulation. The 3D fabrication is followed by a thermal treatment in order to induce in situ generation of metal nanoparticles (NPs) in the polymer matrix. Comprehensive studies were systematically performed on the thermo-mechanical characteristics, morphology and electrical properties of the 3D printed nanocomposites.

Ternary Polymeric Composites Exhibiting Bulk and Surface Quadruple-Shape Memory Properties.

PubMed

Buffington, Shelby Lois; Posnick, Benjamin M; Paul, Justine Elizabeth; Mather, Patrick T

2018-06-19

We report the design and characterization of a multiphase quadruple shape memory composite capable of switching between 4 programmed shapes, three temporary and one permanent. Our approach combined two previously reported fabrication methods by embedding an electrospun mat of PCL in a miscible blend of epoxy monomers and PMMA as a composite matrix. As epoxy polymerization occurred the matrix underwent phase separation between the epoxy and PMMA materials. This created a multiphase composite with PCL fibers and a two-phase matrix composed of phase-separated epoxy and PMMA. The resulting composite demonstrated three separate thermal transitions and amenability to mechanical programming of three separate temporary shapes in addition to one final, equilibrium shape. In addition, quadruple surface shape memory abilities are successfully demonstrated. The versatility of this approach offers a large degree of design flexibility for multi-shape memory materials. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Graphene nanocomposites for electrochemical cell electrodes

DOEpatents

Zhamu, Aruna; Jang, Bor Z.; Shi, Jinjun

2015-11-19

A composite composition for electrochemical cell electrode applications, the composition comprising multiple solid particles, wherein (a) a solid particle is composed of graphene platelets dispersed in or bonded by a first matrix or binder material, wherein the graphene platelets are not obtained from graphitization of the first binder or matrix material; (b) the graphene platelets have a length or width in the range of 10 nm to 10 .mu.m; (c) the multiple solid particles are bonded by a second binder material; and (d) the first or second binder material is selected from a polymer, polymeric carbon, amorphous carbon, metal, glass, ceramic, oxide, organic material, or a combination thereof. For a lithium ion battery anode application, the first binder or matrix material is preferably amorphous carbon or polymeric carbon. Such a composite composition provides a high anode capacity and good cycling response. For a supercapacitor electrode application, the solid particles preferably have meso-scale pores therein to accommodate electrolyte.

Combinatorial and high-throughput approaches in polymer science

NASA Astrophysics Data System (ADS)

Zhang, Huiqi; Hoogenboom, Richard; Meier, Michael A. R.; Schubert, Ulrich S.

2005-01-01

Combinatorial and high-throughput approaches have become topics of great interest in the last decade due to their potential ability to significantly increase research productivity. Recent years have witnessed a rapid extension of these approaches in many areas of the discovery of new materials including pharmaceuticals, inorganic materials, catalysts and polymers. This paper mainly highlights our progress in polymer research by using an automated parallel synthesizer, microwave synthesizer and ink-jet printer. The equipment and methodologies in our experiments, the high-throughput experimentation of different polymerizations (such as atom transfer radical polymerization, cationic ring-opening polymerization and emulsion polymerization) and the automated matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy (MALDI-TOF MS) sample preparation are described.

Nanostructured Drugs Embedded into a Polymeric Matrix: Vinpocetine/PVP Hybrids Investigated by Debye Function Analysis.

PubMed

Hasa, Dritan; Giacobbe, Carlotta; Perissutti, Beatrice; Voinovich, Dario; Grassi, Mario; Cervellino, Antonio; Masciocchi, Norberto; Guagliardi, Antonietta

2016-09-06

Microcrystalline vinpocetine, coground with cross-linked polyvinylpyrrolidone, affords hybrids containing nanosized drug nanocrystals, the size and size distributions of which depend on milling times and drug-to-polymer weight ratios. Using an innovative approach to microstructural characterization, we analyzed wide-angle X-ray total scattering data by the Debye function analysis and demonstrated the possibility to characterize pharmaceutical solid dispersions obtaining a reliable quantitative view of the physicochemical status of the drug dispersed in an amorphous carrier. The microstructural properties derived therefrom have been successfully employed in reconciling the enigmatic difference in behavior between in vitro and in vivo solubility tests performed on nanosized vinpocetine embedded in a polymeric matrix.

Composition and method for polymer moderated catalytic water formation

DOEpatents

Shepodd, Timothy Jon

1999-01-01

A composition suitable for safely removing hydrogen from gaseous mixtures containing hydrogen and oxygen, particularly those mixtures wherein the hydrogen concentration is within the explosive range. The composition comprises a hydrogenation catalyst, preferably Pd dispersed on carbon, wherein the concentration of Pd is from about 1-10 wt %, dispersed in a polymeric material matrix. As well as serving as a matrix to contain the hydrogenation catalyst, the polymeric material, which is substantially unreactive to hydrogen, provides both a diffusion restriction to hydrogen and oxygen, thereby limiting the rate at which the reactants (hydrogen and oxygen) can diffuse to the catalyst surface and thus, the production of heat from the recombination reaction and as a heat sink.

Assembly and Development of the Pseudomonas aeruginosa Biofilm Matrix

PubMed Central

Ma, Luyan; Conover, Matthew; Lu, Haiping; Parsek, Matthew R.; Bayles, Kenneth; Wozniak, Daniel J.

2009-01-01

Virtually all cells living in multicellular structures such as tissues and organs are encased in an extracellular matrix. One of the most important features of a biofilm is the extracellular polymeric substance that functions as a matrix, holding bacterial cells together. Yet very little is known about how the matrix forms or how matrix components encase bacteria during biofilm development. Pseudomonas aeruginosa forms environmentally and clinically relevant biofilms and is a paradigm organism for the study of biofilms. The extracellular polymeric substance of P. aeruginosa biofilms is an ill-defined mix of polysaccharides, nucleic acids, and proteins. Here, we directly visualize the product of the polysaccharide synthesis locus (Psl exopolysaccharide) at different stages of biofilm development. During attachment, Psl is anchored on the cell surface in a helical pattern. This promotes cell–cell interactions and assembly of a matrix, which holds bacteria in the biofilm and on the surface. Chemical dissociation of Psl from the bacterial surface disrupted the Psl matrix as well as the biofilm structure. During biofilm maturation, Psl accumulates on the periphery of 3-D-structured microcolonies, resulting in a Psl matrix-free cavity in the microcolony center. At the dispersion stage, swimming cells appear in this matrix cavity. Dead cells and extracellular DNA (eDNA) are also concentrated in the Psl matrix-free area. Deletion of genes that control cell death and autolysis affects the formation of the matrix cavity and microcolony dispersion. These data provide a mechanism for how P. aeruginosa builds a matrix and subsequently a cavity to free a portion of cells for seeding dispersal. Direct visualization reveals that Psl is a key scaffolding matrix component and opens up avenues for therapeutics of biofilm-related complications. PMID:19325879

Assembly and development of the Pseudomonas aeruginosa biofilm matrix.

PubMed

Ma, Luyan; Conover, Matthew; Lu, Haiping; Parsek, Matthew R; Bayles, Kenneth; Wozniak, Daniel J

2009-03-01

Virtually all cells living in multicellular structures such as tissues and organs are encased in an extracellular matrix. One of the most important features of a biofilm is the extracellular polymeric substance that functions as a matrix, holding bacterial cells together. Yet very little is known about how the matrix forms or how matrix components encase bacteria during biofilm development. Pseudomonas aeruginosa forms environmentally and clinically relevant biofilms and is a paradigm organism for the study of biofilms. The extracellular polymeric substance of P. aeruginosa biofilms is an ill-defined mix of polysaccharides, nucleic acids, and proteins. Here, we directly visualize the product of the polysaccharide synthesis locus (Psl exopolysaccharide) at different stages of biofilm development. During attachment, Psl is anchored on the cell surface in a helical pattern. This promotes cell-cell interactions and assembly of a matrix, which holds bacteria in the biofilm and on the surface. Chemical dissociation of Psl from the bacterial surface disrupted the Psl matrix as well as the biofilm structure. During biofilm maturation, Psl accumulates on the periphery of 3-D-structured microcolonies, resulting in a Psl matrix-free cavity in the microcolony center. At the dispersion stage, swimming cells appear in this matrix cavity. Dead cells and extracellular DNA (eDNA) are also concentrated in the Psl matrix-free area. Deletion of genes that control cell death and autolysis affects the formation of the matrix cavity and microcolony dispersion. These data provide a mechanism for how P. aeruginosa builds a matrix and subsequently a cavity to free a portion of cells for seeding dispersal. Direct visualization reveals that Psl is a key scaffolding matrix component and opens up avenues for therapeutics of biofilm-related complications.

Cell growth and protein expression of Shewanella oneidensis in biofilms and hydrogel-entrapped cultures.

PubMed

Zhang, Yingdan; Ng, Chun Kiat; Cohen, Yehuda; Cao, Bin

2014-05-01

The performance of biofilm-based bioprocesses is difficult to predict and control because of the intrinsic heterogeneous and dynamic properties of microbial biofilms. Biofilm mimics, such as microbial cells entrapped in polymeric scaffolds that are permeable for nutrients, have been proposed to replace real biofilms to achieve long-term robust performance in engineering applications. However, the physiological differences between cells that are physically entrapped in a synthetic polymeric matrix and biofilm cells that are encased in a self-produced polymeric matrix remain unknown. In this study, using Shewanella oneidensis as a model organism and alginate hydrogel as a model synthetic matrix, we compared the cell growth and protein expression in entrapped cultures and biofilms. The hydrogel-entrapped cultures were found to exhibit a growth rate comparable with biofilms. There was no substantial difference in cell viability, surface charge, as well as hydrophobicity between the cells grown in alginate hydrogel and those grown in biofilms. However, the gel-entrapped cultures were found to be physiologically different from biofilms. The gel-entrapped cultures had a higher demand for metabolic energy. The siderophore-mediated iron uptake was repressed in the gel-entrapped cells. The presence of the hydrogel matrix decreased the expression of proteins involved in biofilm formation, while inducing the production of extracellular DNA (eDNA) in the gel-entrapped cultures. These results advance the fundamental understanding of the physiology of hydrogel-entrapped cells, which can lead to more efficient biofilm mimic-based applications.

Factorial Design Based Multivariate Modeling and Optimization of Tunable Bioresponsive Arginine Grafted Poly(cystaminebis(acrylamide)-diaminohexane) Polymeric Matrix Based Nanocarriers.

PubMed

Yang, Rongbing; Nam, Kihoon; Kim, Sung Wan; Turkson, James; Zou, Ye; Zuo, Yi Y; Haware, Rahul V; Chougule, Mahavir B

2017-01-03

Desired characteristics of nanocarriers are crucial to explore its therapeutic potential. This investigation aimed to develop tunable bioresponsive newly synthesized unique arginine grafted poly(cystaminebis(acrylamide)-diaminohexane) [ABP] polymeric matrix based nanocarriers by using L9 Taguchi factorial design, desirability function, and multivariate method. The selected formulation and process parameters were ABP concentration, acetone concentration, the volume ratio of acetone to ABP solution, and drug concentration. The measured nanocarrier characteristics were particle size, polydispersity index, zeta potential, and percentage drug loading. Experimental validation of nanocarrier characteristics computed from initially developed predictive model showed nonsignificant differences (p > 0.05). The multivariate modeling based optimized cationic nanocarrier formulation of <100 nm loaded with hydrophilic acetaminophen was readapted for a hydrophobic etoposide loading without significant changes (p > 0.05) except for improved loading percentage. This is the first study focusing on ABP polymeric matrix based nanocarrier development. Nanocarrier particle size was stable in PBS 7.4 for 48 h. The increase of zeta potential at lower pH 6.4, compared to the physiological pH, showed possible endosomal escape capability. The glutathione triggered release at the physiological conditions indicated the competence of cytosolic targeting delivery of the loaded drug from bioresponsive nanocarriers. In conclusion, this unique systematic approach provides rational evaluation and prediction of a tunable bioresponsive ABP based matrix nanocarrier, which was built on selected limited number of smart experimentation.

HPLC separation of triacylglycerol positional isomers on a polymeric ODS column.

PubMed

Kuroda, Ikuma; Nagai, Toshiharu; Mizobe, Hoyo; Yoshimura, Nobuhito; Gotoh, Naohiro; Wada, Shun

2008-07-01

A polymeric ODS column was applied to the resolution of triacylglycerol positional isomers (TAG-PI), i.e. 1,3-dioleoyl-2-palmitoyl-glycerol (OPO) and 1,2-dioleoyl-3-palmitoyl-rac-glycerol (OOP), with a recycle HPLC system. To investigate the ODS column species and the column temperatures for the resolution of a TAG-PI pair, a mixture of OPO and OOP was subjected to an HPLC system equipped with a non-endcapped polymeric, endcapped monomeric, endcapped intermediate, or non-endcapped monomeric ODS column at three different column temperatures (40, 25, or 10 degrees C). Only the non-endcapped polymeric ODS column achieved the separation of OPO and OOP, and the lowest column temperature (10 degrees C) showed the best resolution for them. The other pair of TAG-PI, a mixture of 1,3-dipalmitoyl-2-oleoyl-glycerol (POP) and 1,2-dipalmitoyl-3-oleoyl-rac-glycerol (PPO) was also subjected to the system equipped with a non-endcapped polymeric or monomeric ODS column at five different column temperatures (40, 32, 25, 17, and 10 degrees C). Thus, POP and PPO were also separated on only the non-endcapped polymeric ODS column at 25 degrees C. However, no clear peak appeared at 10 degrees C. These results would indicate that the polymeric ODS stationary phase has an ability to recognize the structural differences between TAG-PI pairs. Also, the column temperature is a very important factor for separating the TAG-PI pair, and the optimal temperature would relate to the solubility of TAG-PI in the mobile phase. Furthermore, the recycle HPLC system provided measurements for the separation and analysis of TAG-PI pairs.

Molecular simulation and mathematical modelling of glass transition temperature depression induced by CO2 plasticization in Polysulfone membranes

NASA Astrophysics Data System (ADS)

Lock, S. S. M.; Lau, K. K.; Lock Sow Mei, Irene; Shariff, A. M.; Yeong, Y. F.; Bustam, A. M.

2017-08-01

A sequence of molecular modelling procedure has been proposed to simulate experimentally validated membrane structure characterizing the effect of CO2 plasticization, whereby it can be subsequently employed to elucidate the depression in glass transition temperature (Tg ). Based on the above motivation, unswollen and swollen Polysulfone membrane structures with different CO2 loadings have been constructed, whereby the accuracy has been validated through good compliance with experimentally measured physical properties. It is found that the presence of CO2 constitutes to enhancement in polymeric chain relaxation, which consequently promotes the enlargement of molecular spacing and causes dilation in the membrane matrix. A series of glass transition temperature treatment has been conducted on the verified molecular structure to elucidate the effect of CO2 loadings to the depression in Tg induced by plasticization. Subsequently, a modified Michealis-Menten (M-M) function has been implemented to quantify the effect of CO2 loading attributed to plasticization towards Tg .

Heat Stable Polymers: Polyphenylene and Other Aromatic Polymers

DTIC Science & Technology

1977-01-01

crystalline transition temperature . Model reactions on 4- and 6-phienyl-2-pyrones show that this monomer type is unsuitable for the syntheses of... temperature to a rod-like molecule with a high glass transition temperature . The polymerization reaction is acid catalyzed, but is carried out most...Polymerization Reactions...................24 Solution Properties......................27 Phase Transition Temperatures , Thermal Stability and Thermomechanical

Isolation of beta-mannanase from Cocos nucifera Linn haustorium and its application in the depolymerization of beta-(1,4)-linked D-mannans.

PubMed

Soumya, Rema S; Abraham, Emilia T

2010-05-01

Beta-mannanase was extracted from coconut (Cocos nucifera Linn) haustorium and purified through ammonium sulfate precipitation and sepharose 6B-lectin affinity chromatography. Coconut beta-mannanase is an acidic protein with a pI of 3.75. The molecular mass of coconut beta-mannanase (sodium dodecyl sulfate-polyacrylamide gel electrophoresis) was found to be 44 kDa and was confirmed by matrix-assisted laser desorption ionization time-of-flight mass spectrometry. The optimum temperature and pH for enzyme activity was 70 degrees C and 5.2. The enzyme was used for the preparation of neutraceutical dietary supplement from galactomannans of guar gum and tender coconut kernel having a beta-(1,4)-linked D-mannose backbone. Depolymerized guar gum has 92% of oligosaccharides with a degree of polymerization of 3 and 7. Tender coconut kernel has a degree of polymerization of 9-39 oligosaccharides along with disaccharides and trisaccharides. Hence this mannanase will be useful to depolymerize beta-(1,4)-linked D-mannose polysaccharides from most plant sources to produce prebiotics in a cost-effective technique.

Determination of polychlorinated biphenyls in ocean water and bovine milk using crosslinked polymeric ionic liquid sorbent coatings by solid-phase microextraction.

PubMed

Joshi, Manishkumar D; Ho, Tien D; Cole, William T S; Anderson, Jared L

2014-01-01

Crosslinked polymeric ionic liquid (PIL)-based sorbent coatings were employed in the extraction of 21 polychlorinated biphenyls (PCBs) from ocean water and bovine milk using solid-phase microextraction (SPME). The extraction temperature, time, and concentration of sodium chloride added to the matrix were optimized in order to determine the best extraction conditions for the extraction of PCBs. The analytical performance of the crosslinked PIL-based SPME fibers was compared with a commercial 7 µm polydimethylsiloxane (PDMS) fiber using gas chromatography (GC) employing an electron capture detector (ECD) and mass spectrometric detection (MS). Higher sensitivities for PCBs were achieved using PIL-based fibers when compared to PDMS fiber due to the incorporation of benzyl moieties into the PIL structures. The limits of detection (LOD) for all PCBs were determined to be in the low ng L(-1) range using the three studied coatings. Recovery studies were performed for PCBs in ocean water and bovine milk to validate the applicability of the current SPME method. © 2013 Published by Elsevier B.V.

Enhanced thermal and mechanical properties of PLA/MoS2 nanocomposites synthesized via the in-situ ring-opening polymerization

NASA Astrophysics Data System (ADS)

Chen, Pengpeng; Liang, Xiao; Xu, Ying; Zhou, Yifeng; Nie, Wangyan

2018-05-01

In this work, MoS2 nanosheets were employed to reinforce PLA. In order to promote the homogeneous dispersion of MoS2 in PLA and form a strong interface between MoS2 and PLA, the MoS2 nanosheets were firstly modified by mercapto-ethylamine, and then functionalized with PLA chains through ring-opening polymerization of poly(L-lactide). The XRD, XPS, TGA and 1H NMR characterizations confirmed the successful amino and PLA functionalization of MoS2 nanosheets. The obtained MoS2-g-PLA nanosheets were then introduced to reinforce PLA. SEM images displayed that the MoS2-g-PLA nanosheets were dispersed in PLA matrix uniformly. TGA results showed that initial decomposition temperature was improved from 275.6 °C to 334.8 °C with 0.5 wt% of MoS2-g-PLA nanosheets. The storage modulus of PLA/MoS2-g-PLA-0.5 wt% in the glass state and rubber state were both greatly enhanced compared with neat PLA.

Development of brazing process for W-EUROFER joints using Cu-based fillers

NASA Astrophysics Data System (ADS)

de Prado, J.; Sánchez, M.; Ureña, A.

2016-02-01

A successful joint between W and EUROFER using high temperature brazing technique has been achieved for structural application in future fusion power plants. Cu-based powder alloy mixed with a polymeric binder has been used as filler. Microstructural analysis of the joints revealed that the joint consisted mainly of primary phases and acicular structures in a Cu matrix. Interaction between EUROFER and filler took place at the interface giving rise to several Cu-Ti-Fe rich layers. A loss of hardness at the EUROFER substrate close to the joint due to a diffusion phenomenon during brazing cycle was measured; however, the joints had an adequate shear strength value.

Graphite-polyimide composite for application to aircraft engines

NASA Technical Reports Server (NTRS)

Hanson, M. P.; Chamis, C. C.

1974-01-01

A combined experimental and theoretical investigation was performed in order to (1) demonstrate that high quality angleplied laminates can be made from HT-S/PMR-RI (PMR in situ polymerization of monomeric reactants), (2) characterize the PMR-PI material and to determine the HT-S unidirectional composite properties required for composite micro and macromechanics and laminate analyses, and (3) select HT-S/PMR-PI laminate configurations to meet the general design requirements for high-tip-speed compressor blades. The results of the investigation showed that HT-S/PMR laminate configurations can be fabricated which satisfy the high-tip-speed compressor blade design requirements when operating within the temperature capability of the polymide matrix.

Experimental and theoretical investigation of HT-S/PMR-PI composites for application to advanced aircraft engines

NASA Technical Reports Server (NTRS)

Hanson, M. P.; Chamis, C. C.

1973-01-01

Investigations were performed in order to: (1) demonstrate that high quality angleplied laminates can be made from HT-S/PMR-PI (PMR in situ polymerization of monomeric reactants), (2) characterize the PMR-PI material and to determine the HT-S unidirectional composite properties required for composite micro and macromechanics and laminate analyses, and (3) select HT-S/PMR laminate configurations to meet the general design requirements for high-tip-speed compressor blades. The results of the investigation show that HT-S/PMR laminate configurations can be fabricated which satisfy the high-tip-speed compressor blade design requirements when operating within the temperature capability of the polyimide matrix.

Selection of a suitable method for the preparation of polymeric nanoparticles: multi-criteria decision making approach.

PubMed

Krishnamoorthy, Kannan; Mahalingam, Manikandan

2015-03-01

The present study is aimed to select the suitable method for preparation of camptothecin loaded polymeric nanoparticles by utilizing the multi-criteria decision making method. Novel approaches of drug delivery by formulation using nanotechnology are revolutionizing the future of medicine. Recent years have witnessed unprecedented growth of research and application in the area of nanotechnology. Nanoparticles have become an important area of research in the field of drug delivery because they have the ability to deliver a wide range of drug to varying areas of body. Despite of extensive research and development, polymeric nanoparticles are frequently used to improve the therapeutic effect of drugs. A number of techniques are available for the preparation of polymeric nanoparticles. The Analytical Hierarchy Process (AHP) is a method for decision making, which are derived from individual judgements for qualitative factors, using the pair-wise comparison matrix. In AHP, a decision hierarchy is constructed with a goal, criteria and alternatives. The model uses three main criteria 1) Instrument, 2) Process and Output and 3) Cost. In addition, there are eight sub-criteria's as well as eight alternatives. Pair-wise comparison matrixes are used to obtain the overall priority weight and ranking for the selection of suitable method. Nanoprecipitation technique is the most suitable method for the preparation of camptothecin loaded polymeric nanoparticles with the highest overall priority weight of 0.297 CONCLUSION: In particular, the result indicates that the priority weights obtained from AHP could be defined as a multiple output for finding out the most suitable method for preparation of camptothecin loaded polymeric nanoparticles.

2DCOS and PCMW2D analysis of FT-IR/ATR spectra measured at variable temperatures on-line to a polyurethane polymerization

NASA Astrophysics Data System (ADS)

Schuchardt, Patrick; Unger, Miriam; Siesler, Heinz W.

2018-01-01

In the present communication the potential of 2DCOS analysis and the spin-off technique perturbation-correlation moving window 2D (PCMW2D) analysis is illustrated with reference to spectroscopic changes observed in a data set recorded by in-line fiber-coupled FT-IR spectroscopy in the attenuated total reflection (ATR) mode during a polyurethane solution polymerization at different temperatures. In view of the chemical functionalities involved, hydrogen bonding plays an important role in this polymerization reaction. Based on the 2DCOS and PCMW2D analysis, the sequence of hydrogen bonding changes accompanying the progress of polymerization and precipitation of solid polymer can be determined. Complementary to the kinetic data derived from the original variable-temperature spectra in a previous publication the results provide a more detailed picture of the investigated solution polymerization.

Nanoscale High Energetic Materials: A Polymeric Nitrogen Chain N8 Confined inside a Carbon Nanotube

NASA Astrophysics Data System (ADS)

Abou-Rachid, Hakima; Hu, Anguang; Timoshevskii, Vladimir; Song, Yanfeng; Lussier, Louis-Simon

2008-05-01

We present a theoretical study of a new hybrid material, nanostructured polymeric nitrogen, where a polymeric nitrogen chain is encapsulated in a carbon nanotube. The electronic and structural properties of the new system are studied by means of ab initio electronic structure and molecular dynamics calculations. Finite temperature simulations demonstrate the stability of this nitrogen phase at ambient pressure and room temperature using carbon nanotube confinement. This nanostructured confinement may open a new path towards stabilizing polynitrogen or polymeric nitrogen at ambient conditions.

Bio-inspired method to obtain multifunctional dynamic nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kushner, Aaron M.; Guan, Zhibin; Williams, Gregory

A method for a polymeric or nanocomposite material. The method includes assembling a multiphase hard-soft structure, where the structure includes a hard micro- or nano-phase, and a soft micro- or nano-phase that includes a polymeric scaffold. In the method, the polymeric scaffold includes dynamically interacting motifs and has a glass transition temperature (T.sub.g) lower than the intended operating temperature of the material.

Photoinitiated Polymerization-Induced Self-Assembly of Glycidyl Methacrylate for the Synthesis of Epoxy-Functionalized Block Copolymer Nano-Objects.

PubMed

Tan, Jianbo; Liu, Dongdong; Huang, Chundong; Li, Xueliang; He, Jun; Xu, Qin; Zhang, Li

2017-08-01

Herein, a novel photoinitiated polymerization-induced self-assembly formulation via photoinitiated reversible addition-fragmentation chain transfer dispersion polymerization of glycidyl methacrylate (PGMA) in ethanol-water at room temperature is reported. It is demonstrated that conducting polymerization-induced self-assembly (PISA) at low temperatures is crucial for obtaining colloidal stable PGMA-based diblock copolymer nano-objects. Good control is maintained during the photo-PISA process with a high rate of polymerization. The polymerization can be switched between "ON" and "OFF" in response to visible light. A phase diagram is constructed by varying monomer concentration and degree of polymerization. The PGMA-based diblock copolymer nano-objects can be further cross-linked by using a bifunctional primary amine reagent. Finally, silver nanoparticles are loaded within cross-linked vesicles via in situ reduction, exhibiting good catalytic properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photothermal triggering of self-healing processes applied to the reparation of bio-based polymer networks

NASA Astrophysics Data System (ADS)

Altuna, F. I.; Antonacci, J.; Arenas, G. F.; Pettarin, V.; Hoppe, C. E.; Williams, R. J. J.

2016-04-01

Green laser irradiation successfully activated self-healing processes in epoxy-acid networks modified with low amounts of gold nanoparticles (NPs). A bio-based polymer matrix, obtained by crosslinking epoxidized soybean oil (ESO) with an aqueous citric acid (CA) solution, was self-healed through molecular rearrangements produced by transesterification reactions of β-hydroxyester groups generated in the polymerization reaction. The temperature increase required for the triggering of these thermally activated reactions was attained by green light irradiation of the damaged area. Compression force needed to assure a good contact between crack faces was achieved by volume dilatation generated by the same temperature rise. Gold NPs dispersed in the polymer efficiently generated heat in the presence of electromagnetic radiation under plasmon resonance, acting as nanometric heating sources and allowing remote activation of the self-healing in the crosslinked polymer.

Locating a silane coupling agent in silica-filled rubber composites by EFTEM.

PubMed

Dohi, Hidehiko; Horiuchi, Shin

2007-11-20

A silane coupling agent (SA) was added to silica/rubber composites at different mixing temperatures and the formation of a coupling layer at the silica/rubber interface was investigated by energy-filtering transmission electron microscopy. Bis(triethoxysilypropyl)tetrasulfane (TESPT), which was used as the SA, reacted with the silanol groups on the silica surface and with styrene-butadiene rubber to form an interfacial coupling layer. The silicon and sulfur elemental distributions were analyzed by electron energy loss spectroscopy (EELS) and elemental mapping. The amount of TESPT trapped in the rubber matrix could be qualitatively estimated by EELS, and the in situ formed coupling layer could be characterized by elemental mapping. The result indicated that the formation of the coupling layer was affected by the mixing temperature. The technique described here will contribute to the study of interface-property relationships and the evaluation of the role of SAs in polymeric composites.

Silica fume reinforced polystyrene-based composite particles used as ultra-light weight proppants in hydraulic fracturing

NASA Astrophysics Data System (ADS)

Liang, Tian; Yan, Chunjie; Zhou, Sen; Zhang, Yonghan

2017-11-01

A new kind composite particle which could be utilized as ultra-light weight proppant was prepared via suspension polymerization in this work. The composite particles were composed of polystyrene and modified silica fume. This study indicated the composite particles had a bulk density (around 0.65 g cm-3) that is even lower than most of the commercial proppants. The pure polystyrene particles had a glass transition temperature of 130.3 °C and a crushing rate of 5.0% under the pressure of 52 MPa for 3 min. While the heat-treated composite particles had a higher glass transition temperature of 146.1 °C and a lower crushing rate of 1.0% under the same testing condition. In addition, the processes of synthesizing composite particles, procedures of heat treatment, effects of different incorporation amount and dispersion of modified silica fume in polymer matrix were systematically investigated.

Biocomposites from co-polypropylene and distillers' grains

NASA Astrophysics Data System (ADS)

Zarrinbakhsh, Nima; Mohanty, Amar K.; Misra, Manjusri

2015-05-01

In the present work, we have explored the polymeric composites of distillers' grains with co-polypropylene (co-PP). The effect of maleated-PP compatibilizer on mechanical, thermomechanical and physical properties was evaluated. The composite materials were produced by melt extrusion in a micro-compounder followed by injection molding in a micro-injection machine. The composites were characterized for their tensile, flexural and impact properties. Also, melt flow index and heat deflection temperature were measured. The results showed more than 30 % improvement in modulus when comparing the compatibilized biocomposite with neat co-PP. Also, the strength of the compatibilized biocomposite measured in tensile and flexural tests was comparable to or even better than that of the neat matrix. On the other hand, the reduced flexibility and toughness as a result of compatibilization were in an acceptable range. The biocomposites showed more rigidity at elevated temperatures. The produced distillers' grain biocomposites showed promises for industrial applications.

Ziegler-Natta Catalyst Based on MgCl₂/Clay/ID/TiCl₄ for the Synthesis of Spherical Particles of Polypropylene Nanocomposites.

PubMed

Cardoso, Renata da Silva; Oliveira, Jaqueline da Silva; Ramis, Luciana Bortolin; Marques, Maria de Fátima V

2018-07-01

In the present work, we have designed MgCl2/clay/internal donor (ID)/TiCl4 based bisupported Ziegler-Natta catalysts containing varying amounts of organoclay (montmorillonite) in order to synthesize spherical particles of polypropylene/clay nanocomposites (PCN). The organoclay was introduced into the catalyst support formulation and PCN was obtained using the in situ polymerization technique. Decreasing the reaction time, it was possible to obtain nanocomposites with high concentrations of clay (masterbatches). Micrographs of SEM confirmed the spherical morphology of the catalysts. In addition, XRD patterns show that the active sites for polymerization were inserted in the clay galleries. The catalytic performance was evaluated in slurry propylene polymerization using triethylaluminium as cocatalyst and silane as external electron donor at 70 °C, 4 bar, and different reaction times. The PCNs obtained containing different clay amounts were characterized by X-ray diffraction, thermal analyses, transmission electronic microscopy, and extractables in heptane. The results revealed that the synthesized PP/clay particles were also spherical showing that the morphological control is possible even using catalysts containing high amounts of clay. The PCN presented high degradation temperature (459 °C). The XRD peak related to the clay interlamellar distance has shifted to lower angles, and TEM images confirmed the formation of exfoliated/intercalated clay on the PP matrix and absence of microparticles of clay.

Nonequilibrium material effects on the behavior of polymeric composite matrices and their related composites

NASA Technical Reports Server (NTRS)

Wilkes, G. L.

1982-01-01

The effects of physical aging on the material properties of some linear and network macromolecular glasses are discussed. The free volume concept is used to describe this behavior. The effect of physical aging on properties of some uniaxial graphite/fiber epoxy resin composites is investigated using stress relaxation in both tensile and flexural modes. The matrix polymers used were resins both of which are based on a 4,4-methylenedianiline derivative of epichlorohydrin with diamino diphenyl sulfone (DDS) as the curing agent. The matrix resin, as used in the practical application in composites, not fully cured and the glass transition of the network was dependent on the curing schedule. The physical aging of the bulk crosslinked epoxy was found to depend on the annealing temperature, and the T sub g of the resin. The physical aging of the composite, monitored by the stress relaxation method, was found to be dependent on the testing direction.

Method for preparing dielectric composite materials

DOEpatents

Lauf, Robert J.; Anderson, Kimberly K.; Montgomery, Frederick C.; Collins, Jack L.; Felten, John J.

2004-11-23

The invention allows the fabrication of small, dense beads of dielectric materials with selected compositions, which are incorporated into a polymeric matrix for use in capacitors, filters, and the like. A porous, generally spherical bead of hydrous metal oxide containing titanium or zirconium is made by a sol-gel process to form a substantially rigid bead having a generally fine crystallite size and correspondingly finely distributed internal porosity. The resulting gel bead may be washed and hydrothermally reacted with a soluble alkaline earth salt (typically Ba or Sr) at elevated temperature and pressure to convert the bead into a mixed hydrous titanium- or zirconium-alkaline earth oxide while retaining the generally spherical shape. Alternatively, the gel bead may be made by coprecipitation. This mixed oxide bead is then washed, dried and calcined to produce the desired (BaTiO.sub.3, PbTiO.sub.3, SrZrO.sub.3) structure. The sintered beads are incorporated into a selected polymer matrix. The resulting dielectric composite material may be electrically "poled" if desired.

Dielectric composite materials and method for preparing

DOEpatents

Lauf, Robert J.; Anderson, Kimberly K.; Montgomery, Frederick C.; Collins, Jack L.; Felten, John J.

2003-07-29

The invention allows the fabrication of small, dense beads of dielectric materials with selected compositions, which are incorporated into a polymeric matrix for use in capacitors, filters, and the like. A porous, generally spherical bead of hydrous metal oxide containing titanium or zirconium is made by a sol-gel process to form a substantially rigid bead having a generally fine crystallite size and correspondingly finely distributed internal porosity. The resulting gel bead may be washed and hydrothermally reacted with a soluble alkaline earth salt (typically Ba or Sr) at elevated temperature and pressure to convert the bead into a mixed hydrous titanium- or zirconium-alkaline earth oxide while retaining the generally spherical shape. Alternatively, the gel bead may be made by coprecipitation. This mixed oxide bead is then washed, dried and calcined to produce the desired (BaTiO.sub.3, PbTiO.sub.3, SrZrO.sub.3) structure. The sintered beads are incorporated into a selected polymer matrix. The resulting dielectric composite material may be electrically "poled" if desired.

Composition and apparatus for detecting gamma radiation

DOEpatents

Hofstetter, Kenneth J.

1994-01-01

A gamma radiation detector and a radioluminiscent composition for use therein. The detector includes a radioluminscent composition that emits light in a characteristic wavelength region when exposed to gamma radiation, and means for detecting said radiation. The composition contains a scintillant such as anglesite (PbSO.sub.4) or cerussite (PbCO.sub.3) incorporated into an inert, porous glass matrix via a sol-gel process. Particles of radiation-sensitive scintillant are added to, a sol solution. The mixture is polymerized to form a gel, then dried under conditions that preserve the structural integrity and radiation sensitivity of the scintillant. The final product is a composition containing the uniformly-dispersed scintillant in an inert, optically transparent and highly porous matrix. The composition is chemically inert and substantially impervious to environmental conditions including changes in temperature, air pressure, and so forth. It can be fabricated in cylinders, blocks with holes therethrough for flow of fluid, sheets, surface coatings, pellets or other convenient shapes.

Composition and apparatus for detecting gamma radiation

DOEpatents

Hofstetter, K.J.

1994-08-09

A gamma radiation detector and a radioluminescent composition for use therein. The detector includes a radioluminescent composition that emits light in a characteristic wavelength region when exposed to gamma radiation, and means for detecting said radiation. The composition contains a scintillant such as anglesite (PbSO[sub 4]) or cerussite (PbCO[sub 3]) incorporated into an inert, porous glass matrix via a sol-gel process. Particles of radiation-sensitive scintillant are added to, a sol solution. The mixture is polymerized to form a gel, then dried under conditions that preserve the structural integrity and radiation sensitivity of the scintillant. The final product is a composition containing the uniformly-dispersed scintillant in an inert, optically transparent and highly porous matrix. The composition is chemically inert and substantially impervious to environmental conditions including changes in temperature, air pressure, and so forth. It can be fabricated in cylinders, blocks with holes therethrough for flow of fluid, sheets, surface coatings, pellets or other convenient shapes. 3 figs.

Electrochemical sample matrix elimination for trace-level potentiometric detection with polymeric membrane ion-selective electrodes.

PubMed

Chumbimuni-Torres, Karin Y; Calvo-Marzal, Percy; Wang, Joseph; Bakker, Eric

2008-08-01

Potentiometric sensors are today sufficiently well understood and optimized to reach ultratrace level (subnanomolar) detection limits for numerous ions. In many cases of practical relevance, however, a high electrolyte background hampers the attainable detection limits. A particularly difficult sample matrix for potentiometric detection is seawater, where the high saline concentration forms a major interfering background and reduces the activity of most trace metals by complexation. This paper describes for the first time a hyphenated system for the online electrochemically modulated preconcentration and matrix elimination of trace metals, combined with a downstream potentiometric detection with solid contact polymeric membrane ion-selective microelectrodes. Following the preconcentration at the bismuth-coated electrode, the deposited metals are oxidized and released to a medium favorable to potentiometric detection, in this case calcium nitrate. Matrix interferences arising from the saline sample medium are thus circumvented. This concept is successfully evaluated with cadmium as a model trace element and offers potentiometric detection down to low parts per billion levels in samples containing 0.5 M NaCl background electrolyte.

Electrochemical Sample Matrix Elimination for Trace Level Potentiometric Detection with Polymeric Membrane Ion-Selective Electrodes

PubMed Central

Chumbimuni-Torres, Karin Y.; Calvo-Marzal, Percy; Wang, Joseph; Bakker, Eric

2008-01-01

Potentiometric sensors are today sufficiently well understood and optimized to reach ultra-trace level (sub-nanomolar) detection limits for numerous ions. In many cases of practical relevance, however, a high electrolyte background hampers the attainable detection limits. A particularly difficult sample matrix for potentiometric detection is seawater, where the high saline concentration forms a major interfering background and reduces the activity of most trace metals by complexation. This paper describes for the first time a hyphenated system for the online electrochemically modulated preconcentration and matrix elimination (EMPM) of trace metals, combined with a downstream potentiometric detection with solid contact polymeric membrane ion-selective microelectrodes. Following the preconcentration at the bismuth coated electrodes, the deposited metals are oxidized and released to a medium favorable to potentiometric detection, in this case calcium nitrate. Matrix interferences arising from the saline sample medium are thus circumvented. This concept is successfully evaluated with cadmium as a model trace element and offers potentiometric detection down to low parts per billion levels in samples containing 0.5 M NaCl background electrolyte. PMID:18570385

Effects of ultraviolet irradiation on bonding strength between Co-Cr alloy and citric acid-crosslinked gelatin matrix.

PubMed

Inoue, Motoki; Sasaki, Makoto; Katada, Yasuyuki; Taguchi, Tetsushi

2014-02-01

Novel techniques for creating a strong bond between polymeric matrices and biometals are required. We immobilized polymeric matrices on the surface of biometal for drug-eluting stents through covalent bond. We performed to improve the bonding strength between a cobalt-chromium alloy and a citric acid-crosslinked gelatin matrix by ultraviolet irradiation on the surface of cobalt-chromium alloy. The ultraviolet irradiation effectively generated hydroxyl groups on the surface of the alloy. The bonding strength between the gelatin matrix and the alloy before ultraviolet irradiation was 0.38 ± 0.02 MPa, whereas it increased to 0.48 ± 0.02 MPa after ultraviolet irradiation. Surface analysis showed that the citric acid derivatives occurred on the surface of the cobalt-chromium alloy through ester bond. Therefore, ester bond formation between the citric acid derivatives active esters and the hydroxyl groups on the cobalt-chromium alloy contributed to the enhanced bonding strength. Ultraviolet irradiation and subsequent immobilization of a gelatin matrix using citric acid derivatives is thus an effective way to functionalize biometal surfaces.

Effects of elevated temperature on the viscoplastic modeling of graphite/polymeric composites

NASA Technical Reports Server (NTRS)

Gates, Thomas S.

1991-01-01

To support the development of new materials for the design of next generation supersonic transports, a research program is underway at NASA to assess the long term durability of advanced polymer matrix composites (PMC's). One of main objectives of the program was to explore the effects of elevated temperature (23 to 200 C) on the constitutive model's material parameters. To achieve this goal, test data on the observed nonlinear, stress-strain behavior of IM7/5260 and IM7/8320 composites under tension and compression loading were collected and correlated against temperature. These tests, conducted under isothermal conditions using variable strain rates, included such phenomena as stress relaxation and short term creep. The second major goal was the verification of the model by comparison of analytical predictions and test results for off axis and angle ply laminates. Correlation between test and predicted behavior was performed for specimens of both material systems over a range of temperatures. Results indicated that the model provided reasonable predictions of material behavior in load or strain controlled tests. Periods of loading, unloading, stress relaxation, and creep were accounted for.

Modeling of lipase catalyzed ring-opening polymerization of epsilon-caprolactone.

PubMed

Sivalingam, G; Madras, Giridhar

2004-01-01

Enzymatic ring-opening polymerization of epsilon-caprolactone by various lipases was investigated in toluene at various temperatures. The determination of molecular weight and structural identification was carried out with gel permeation chromatography and proton NMR, respectively. Among the various lipases employed, an immobilized lipase from Candida antartica B (Novozym 435) showed the highest catalytic activity. The polymerization of epsilon-caprolactone by Novozym 435 showed an optimal temperature of 65 degrees C and an optimum toluene content of 50/50 v/v of toluene and epsilon-caprolactone. As lipases can degrade polyesters, a maximum in the molecular weight with time was obtained due to the competition of ring opening polymerization and degradation by specific chain end scission. The optimum temperature, toluene content, and the variation of molecular weight with time are consistent with earlier observations. A comprehensive model based on continuous distribution kinetics was developed to model these phenomena. The model accounts for simultaneous polymerization, degradation and enzyme deactivation and provides a technique to determine the rate coefficients for these processes. The dependence of these rate coefficients with temperature and monomer concentration is also discussed.

Different mechanisms at different temperatures for the ring-opening polymerization of lactide catalyzed by binuclear magnesium and zinc alkoxides.

PubMed

Sun, Yangyang; Cui, Yaqin; Xiong, Jiao; Dai, Zhongran; Tang, Ning; Wu, Jincai

2015-10-07

Two binuclear magnesium and zinc alkoxides supported by a bis-salalen type dinucleating heptadentate Schiff base ligand were synthesized and fully characterized. The two complexes are efficient initiators for the ring-opening polymerization (ROP) of L-lactide, affording polymers with narrow polydispersities and desirable molecular weights. Interestingly, the mechanisms for the ROP of lactide are different at different temperatures. At a high temperature of 130 °C, a coordination-insertion mechanism is reasonable for the bulk melt polymerization of lactide. At a low temperature, the alkoxide cannot initiate the ROP reaction; however, upon the addition of external benzyl alcohol into the system, the ROP of lactide can smoothly proceed via an "activated monomer" mechanism. In addition, these complexes display slight stereo-selectivity for the ring-opening polymerization of rac-lactide, affording partially isotactic polylactide in toluene with a Pm value of 0.59.

Silk fibroin-Thelebolan matrix: A promising chemopreventive scaffold for soft tissue cancer.

PubMed

Mukhopadhyay, Sourav K; Naskar, Deboki; Bhattacharjee, Promita; Mishra, Abheepsa; Kundu, Subhas C; Dey, Satyahari

2017-07-01

Research of improved functional bio-mimetic matrix for regenerative medicine is currently one of the rapidly growing fields in tissue engineering and medical sciences. This study reports a novel bio-polymeric matrix, which is fabricated using silk protein fibroin from Bombyx mori silkworm and fungal exopolysaccharide Thelebolan from Antarctic fungus Thelebolus sp. IITKGP-BT12 by solvent evaporation and freeze drying method. Natural cross linker genipin is used to imprison the Thelebolan within the fibroin network. Different cross-linked and non-cross-linked fibroin/Thelebolan matrices are fabricated and biophysically characterized. Cross-linked thin films show robustness, good mechanical strength and high temperature stability in comparison to non-cross-linked and pure matrices. The 3D sponge matrices demonstrate good cytocompatibility. Interestingly, sustained release of the Thelebolan from the cross-linked matrices induce apoptosis in colon cancer cell line (HT-29) in time dependent manner while it is nontoxic to the normal fibroblast cells (L929).The findings indicate that the cross-linked fibroin/Thelebolan matrices can be used as potential topical chemopreventive scaffold for preclusion of soft tissue carcinoma. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface modification of aramid fibers by bio-inspired poly(dopamine) and epoxy functionalized silane grafting.

PubMed

Sa, Rina; Yan, Yan; Wei, Zhenhai; Zhang, Liqun; Wang, Wencai; Tian, Ming

2014-12-10

A novel biomimetic surface modification method for meta-aramid (MPIA) fibers and the improvement on adhesion with rubber matrix was demonstrated. Inspired by the composition of adhesive proteins in mussels, we used dopamine (DOPA) self-polymerization to form thin, surface-adherent poly(dopamine) (PDA) films onto the surface of MPIA fibers simply by immersing MPIA fibers in a dopamine solution at room temperature. An epoxy functionalized silane (KH560) grafting was then carried out on the surface of the poly(dopamine)-coated MPIA, either by a "one-step" or "two-step" method, to introduce an epoxy group onto the MPIA fiber surface. The surface composition and microstructure of the modified MPIA was characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The results indicated successful grafting of KH560 on the PDA-coated MPIA surface. A single-fiber pull-out test was applied to evaluate the adhesion of MPIA fibers with the rubber matrix. Compared with the untreated MPIA fibers, the adhesion strength between the modified MPIA fibers by "one step" method with rubber matrix has an increase of 62.5%.

Fungal degradation of fiber-reinforced composite materials

NASA Technical Reports Server (NTRS)

Gu, J. D.; Lu, C.; Mitchell, R.; Thorp, K.; Crasto, A.

1997-01-01

As described in a previous report, a fungal consortium isolated from degraded polymeric materials was capable of growth on presterilized coupons of five composites, resulting in deep penetration into the interior of all materials within five weeks. Data describing the utilization of composite constituents as nutrients for the microflora are described in this article. Increased microbial growth was observed when composite extract was incubated with the fungal inoculum at ambient temperatures. Scanning electron microscopic observation of carbon fibers incubated with a naturally developed population of microorganisms showed the formation of bacterial biofilms on the fiber surfaces, suggesting possible utilization of the fiber chemical sizing as carbon and energy sources. Electrochemical impedance spectroscopy was used to monitor the phenomena occurring at the fiber-matrix interfaces. Significant differences were observed between inoculated and sterile panels of the composite materials. A progressive decline in impedance was detected in the inoculated panels. Several reaction steps may be involved in the degradation process. Initial ingress of water into the resin matrix appeared to be followed by degradation of fiber surfaces, and separation of fibers from the resin matrix. This investigation suggested that composite materials are susceptible to microbial attack by providing nutrients for growth.

Effects of High-Temperature-Pressure Polymerized Resin-Infiltrated Ceramic Networks on Oral Stem Cells

PubMed Central

Nassif, Ali; Berbar, Tsouria; Le Goff, Stéphane; Berdal, Ariane; Sadoun, Michael; Fournier, Benjamin P. J.

2016-01-01

Objectives The development of CAD—CAM techniques called for new materials suited to this technique and offering a safe and sustainable clinical implementation. The infiltration of resin in a ceramic network under high pressure and high temperature defines a new class of hybrid materials, namely polymer infiltrated ceramics network (PICN), for this purpose which requires to be evaluated biologically. We used oral stem cells (gingival and pulpal) as an in vitro experimental model. Methods Four biomaterials were grinded, immersed in a culture medium and deposed on stem cells from dental pulp (DPSC) and gingiva (GSC): Enamic (VITA®), Experimental Hybrid Material (EHM), EHM with initiator (EHMi) and polymerized Z100™ composite material (3M®). After 7 days of incubation; viability, apoptosis, proliferation, cytoskeleton, inflammatory response and morphology were evaluated in vitro. Results Proliferation was insignificantly delayed by all the tested materials. Significant cytotoxicity was observed in presence of resin based composites (MTT assay), however no detectable apoptosis and some dead cells were detected like in PICN materials. Cell morphology, major cytoskeleton and extracellular matrix components were not altered. An intimate contact appeared between the materials and cells. Clinical Significance The three new tested biomaterials did not exhibit adverse effects on oral stem cells in our experimental conditions and may be an interesting alternative to ceramics or composite based CAD—CAM blocks. PMID:27196425

Polymerization of perfluorobutadiene

NASA Technical Reports Server (NTRS)

Newman, J.; Toy, M. S.

1970-01-01

Diisopropyl peroxydicarbonate dissolved in liquid perfluorobutadiene is conducted in a sealed vessel at the autogenous pressure of polymerization. Reaction temperature, ratio of catalyst to monomer, and amount of agitation determine degree of polymerization and product yield.

Size matters: smart copolymeric nanohydrogels: synthesis and applications.

PubMed

Katime, Issa; Guerrero, Luis Guillermo; Mendizabal, Eduardo

2012-01-01

In this work the synthesis of smart nanoparticles capable of respond to external stimulus (pH and temperature variations) is reported. To avoid post-polymerization modification, functionalized monomers able to respond to pH and temperature changes were and then polymerized. The synthesized monomers have the capability for coupling with folic acid which is the target molecule. For this reason their polymers can be used as targeted drug delivery systems. Smart polymeric nanoparticles were prepared by direct and inverse microemulsion polymerization of the synthesized monomers. The nanoparticles were charged with drugs and their release kinetic was studied.

Electrodes for sealed secondary batteries

NASA Technical Reports Server (NTRS)

Boies, D. B.; Child, F. T.

1972-01-01

Self-supporting membrane electrode structures, in which active ingredients and graphite are incorporated in a polymeric matrix, improve performance of electrodes in miniature, sealed, alkaline storage batteries.

Biological and nano-indentation properties of polybenzoxazine-based composites reinforced with zirconia particles as a novel biomaterial.

PubMed

Lotfi, L; Javadpour, J; Naimi-Jamal, M R

2018-01-01

The biological and mechanical properties of substances are relevant to their application as biomaterials and there are many efforts to enhance biocompatibility and mechanical properties of bio-medical materials. In this study, to achieve a low rate of shrinkage during polymerization, good mechanical properties, and excellent biocompatibility, benzoxazine based composites were synthesized. Benzoxazine monomer was synthesized using a solventless method. FTIR and DSC analysis were carried out to determine the appropriate polymerization temperature. The low viscosity of the benzoxazine monomer at 70°C attract us to use in situ polymerization after high speed ball milling of the benzoxazine and it mixture with different weight fractions of zirconia particles. Dispersion and adhesion between the ceramic and polymer components were evaluate by SEM. To evaluate the biological properties and toxicity of the polybenzoxazine-based composite samples reinforced with zirconia particles, 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide assay was conducted. The micromechanical properties of each composite were evaluated by more than 20 nanoindentation tests and 3 nanoscratching tests. Surface topography of scratched regions was investigated using Atomic Force Microscopy. Shrinkage was simulated by Materials Studio software. SEM images showed good dispersion and adhesion between the ceramic and polymer components. Biocompatibility assay showed excellent in vitro biocompatibility. Nano-indentation force-displacement curves showed matrix, reinforcement and interphase regions in specimens and excellent homogeneity in mechanical properties. The nanoindentation results showed that the addition of zirconia particles to the polybenzoxazine matrix increased the modulus and hardness of the neat polybenzoxazine; however, by adding more than an optimum level of reinforcement particles, the mechanical properties decreased due to the agglomeration of reinforcement particles and weak interphase that cause inappropriate load transferring between matrix and reinforcement particles. Results of nano-scratching tests showed effects of zirconia particles as reinforcement on the coeffiecient of friction of the synthesized composites. Shrinkage simulation showed a low rate of shrinkage for polybenzoxazine in comparison with other low shrinkage polymers, such as Bis-GMA. Polybenzoxazine based composites that reinforced with an optimum amount of zirconia particles (60% wt micro and 10% wt nano-particles) could be used as a novel biomaterial duo to its excellent biocompatibility, good mechanical properties, appropriate viscosity and low rate of polymeization shrinkage.

Temperature rise in ion-leachable cements during setting reaction.

PubMed

Kanchanavasita, W; Pearson, G J; Anstice, H M

1995-11-01

Resin-modified ion-leachable cements have been developed for use as aesthetic restorative materials. Their apparent improved physical and handling properties can make them more attractive for use than conventional glass-ionomers. However, they contain monomers which are known to contract on polymerization and produce a polymerization exotherm. This study evaluated the temperature rise during setting and the rate of dimensional change of several ion-leachable materials. The resin-modified ion-leachable cements demonstrated greater temperature rises and higher rates of contraction than conventional materials. Generally, the behaviour of these resin-modified materials was similar to that of composite resins. However, some resin-modified cements produced a temperature rise of up to 20 degrees C during polymerization which was greater than that of the composite resin. This temperature rise must be taken into account when using the materials in direct contact with dentine in deep cavities without pulp protection. Longer irradiation time than the recommended 20 s did not significantly increase the maximum temperature rise but slightly extended the time before the temperature started to decline. The temperature of the environment had a significant effect on the rate of dimensional change in some materials. The rate of polymerization contraction of light-activated cements was directly related to the observed temperature rise.

Polymer functionalized single-walled carbon nanotube composites and semi-fluorinated quaternary ammonium polymer colloids and coatings

NASA Astrophysics Data System (ADS)

Paul, Abhijit

Scope and Method of Study: Current study focused on understanding of "wetting" and "dewetting" phenomena between surfaces of single-walled carbon nanotubes (SWCNT) which are lightly grafted with polymer chains by reversible-deactivation radical polymerization, when they are mixed with matrix chains of the same architecture as grafts. Effects of grafts to matrix chain lengths on SWCNT dispersion in matrix polymers were studied by measuring electrical conductivity, glass transition temperature, and storage and loss moduli of nanocomposites. Another area of work was to design semi-fluorinated copolymers with core-shell morphology by emulsion polymerization, study their catalytic activities for hydrolyses of Paraoxon, a toxic insecticide, in the forms of both colloidal dispersions and films, and to characterize the surfaces of the films by atomic force microscopy and by dynamic contact angle measurements. Findings and Conclusions: The glass transition temperature ( Tg) of polystyrene (PS) filled with SWCNT grafted with PS of different lengths increased from 99 to 109 °C at 6 wt% of SWCNT followed by a plateau. The heat capacity (DeltaCp ) at Tg continued to decrease only for the smallest chain length grafted PS nanocomposites. SWCNT/PS nanocomposites had low electrical conductivity and showed no percolation threshold due to the thick polymer coatings. A key finding was that the SWCNT surface can accommodate only a fixed numbers of styrene units. Similar results on change in Tg were obtained for SWCNT/PMMA nanocomposites when molecular weight of matrix (Mmatrix) ≥ molecular weight of grafts (Mgraft). No change in DeltaCp was observed for SWCNT/PMMA nanocomposites. "Wetting" to "dewetting" occurred Mmatrix/ Mgraft ≈ 1. For Mmatrix > Mgraft, electrical conductivity of nanocomposites reached the value of 10-9 S cm-1 at 1.0 wt% nanotube loading and had percolation threshold of electrical conductivity at ˜0.25 wt% SWCNT. Raman and UV-vis-NIR data confirmed that grafting methods have little effect on inherent electronic properties of SWCNT. A key observation was that the behavior of polymer-SWCNT composites is analogous to polymer thin films containing two different lengths of chemically same polymers. On the other hand, semifluorinated copolymers had hydrophobic and lipophilic properties similar to homopolymers of poly(perfluoroalkyl methacrylates), but were not active in detoxification of Paraoxon. Therefore, semi-fluorinated latexes can either act as phase transfer catalysts for hydrolysis of organophosporous compounds or repel the compound, but cannot do both.

Amorphous silicon and organic thin film transistors for electronic applications

NASA Astrophysics Data System (ADS)

Zhou, Lisong

Recently, flexible thin film electronics has attracted huge research interest, and as now, many prototypes are being developed and demonstrated by companies around the world, including displays, logic circuit, and solar cells. Flexible electronics offers many potential advantages: it can not only generate new functions like flexible displays or solar cells, also allow very low cost manufacturing through the use of cheap polymeric substrates and roll-to-roll fabrication. a-Si:H TFT fabrications are compatible with flexible polyimide substrate materials. With the interests in the space environment, for the first time, we tested the performance changes of flexible a-Si:H TFTs, on polyimide substrates, due to irradiation and mechanical stress. Significant changes were found on TFTs after irradiation with fast electrons, which, however, was essentially removed by post-irradiation thermal annealing. On the other hand, few changes were found in TFTs by mechanical stress. These preliminary results indicate that it can be readily engineered for space applications. Furthermore, for the first time, we designed and fabricated ungated n+ muC-Si and gated a-Si:H strain sensors on flexible polyimide substrates. Compared with commercial metallic foil strain sensors, ungated muC-Si sensors and gated a-Si:H sensors are two orders of magnitude smaller in area and consume two orders or magnitude less power. Integration with a-Si:H TFTs can also allow large arrays of strain sensors to be fabricated. To take advantage of lower glass-transition-temperature polymeric substrate materials, reduced processing temperature is desired. The 150°C low-temperature deposition process is achieved by using hydrogen dilution in the PECVD process. The TFT performance and bias stability property are tested similar to that of a 250°C process. These results suggest its viability for practical applications. For even lower process temperature, we have considered organic TFTs. As a practical demonstration, we integrated pentacene TFTs with OLEDs in a simple display. Pentacene TFT passivation techniques were researched, and a PVA and parylene bilayer structure was used. We designed and demonstrated 48 x 48-pixel active matrix OTFTOLED displays, and to our best knowledge, they are the largest on glass substrates and the first on flexible PET substrates. Device performance, uniformity and stability are also compared. These results demonstrate that pentacene TFTs are viable candidates for active-matrix OLED displays and other flexible electronics applications.

Disintegration of nano-embedded microparticles after deposition on mucus: A mechanistic study.

PubMed

Ruge, Christian A; Bohr, Adam; Beck-Broichsitter, Moritz; Nicolas, Valérie; Tsapis, Nicolas; Fattal, Elias

2016-03-01

The conversion of colloidal drug carriers/polymeric nanoparticles into dry microparticulate powders (e.g., by spray-drying) is a prominent approach to overcome the aerodynamic limitations of these formulations for delivery via inhalation. However, to what extent such nano-embedded microparticles disintegrate into individual/intact nanoparticles after contacting relevant physiological media has so far not been addressed. Polymeric nanoparticles were spray-dried into nano-embedded microparticles (NEMs) using different amounts of trehalose as embedding matrix excipient. Formulations were characterized and then evaluated for their disintegration behavior after aerosolization onto model mucus. Although a rapid and complete aqueous redispersion was observed for specific excipient/nanoparticle weight ratios (i.e., greater than 1/1), the same formulations revealed no disintegration after deposition onto a static mucus layer. Double-labeled NEMs powders (i.e., dual color staining of polymeric nanoparticles and trehalose) demonstrated rapid matrix dissolution, while the nanoparticle aggregates persisted. When deposited onto agitated mucus, however, sufficient disintegration of NEMs into individual polymeric nanoparticles was observed. These findings indicate that mechanical forces are necessary to overcome the attraction between individual nanoparticles found within the NEMs. Thus, it remains questionable whether the lung mechanics (e.g., breathing, mucociliary clearance) acting on these formulations will contribute to the overall disintegration process. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of amine structure on CO2 capture by polymeric membranes.

PubMed

Taniguchi, Ikuo; Kinugasa, Kae; Toyoda, Mariko; Minezaki, Koki

2017-01-01

Poly(amidoamine)s (PAMAMs) incorporated into a cross-linked poly(ethylene glycol) exhibited excellent CO 2 separation properties over H 2 . However, the CO 2 permeability should be increased for practical applications. Monoethanolamine (MEA) used as a CO 2 determining agent in the current CO 2 capture technology at demonstration scale was readily immobilized in poly(vinyl alcohol) (PVA) matrix by solvent casting of aqueous mixture of PVA and the amine. The resulting polymeric membranes can be self-standing with the thickness above 3 μm and the amine fraction less than 80 wt%. The gas permeation properties were examined at 40 °C and under 80% relative humidity. The CO 2 separation performance increased with increase of the amine content in the polymeric membranes. When the amine fraction was 80 wt%, the CO 2 permeability coefficient of MEA containing membrane was 604 barrer with CO 2 selectivity of 58.5 over H 2 , which was much higher than the PAMAM membrane (83.7 barrer and 51.8, respectively) under the same operation conditions. On the other hand, ethylamine (EA) was also incorporated into PVA matrix to form a thin membrane. However, the resulting polymeric membranes exhibited slight CO 2 -selective gas permeation properties. The hydroxyl group of MEA was crucial for high CO 2 separation performance.

Effect of amine structure on CO2 capture by polymeric membranes

PubMed Central

Taniguchi, Ikuo; Kinugasa, Kae; Toyoda, Mariko; Minezaki, Koki

2017-01-01

Abstract Poly(amidoamine)s (PAMAMs) incorporated into a cross-linked poly(ethylene glycol) exhibited excellent CO2 separation properties over H2. However, the CO2 permeability should be increased for practical applications. Monoethanolamine (MEA) used as a CO2 determining agent in the current CO2 capture technology at demonstration scale was readily immobilized in poly(vinyl alcohol) (PVA) matrix by solvent casting of aqueous mixture of PVA and the amine. The resulting polymeric membranes can be self-standing with the thickness above 3 μm and the amine fraction less than 80 wt%. The gas permeation properties were examined at 40 °C and under 80% relative humidity. The CO2 separation performance increased with increase of the amine content in the polymeric membranes. When the amine fraction was 80 wt%, the CO2 permeability coefficient of MEA containing membrane was 604 barrer with CO2 selectivity of 58.5 over H2, which was much higher than the PAMAM membrane (83.7 barrer and 51.8, respectively) under the same operation conditions. On the other hand, ethylamine (EA) was also incorporated into PVA matrix to form a thin membrane. However, the resulting polymeric membranes exhibited slight CO2-selective gas permeation properties. The hydroxyl group of MEA was crucial for high CO2 separation performance. PMID:29383045

Supramolecular intermediates in the synthesis of polymeric carbon nitride from melamine cyanurate

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dante, Roberto C., E-mail: rcdante@yahoo.com; Sánchez-Arévalo, Francisco M.; Chamorro-Posada, Pedro

The adduct of melamine and cyanuric acid (MCA) was used in past research to produce polymeric carbon nitride and precursors. The reaction yield was considerably incremented by the addition of sulfuric acid. The polymeric carbon nitride formation occurs around 450 °C at temperatures above the sublimation of the adduct components, which occurs around 400 °C. In this report the effect of sulfuric acid on MCA was investigated. It was found that the MCA rosette supramolecular channel structures behave as a solid solvent able to host small molecules, such as sulfuric acid, inside these channels and interact with them. Therefore, themore » sulfuric acid effect was found to be close to that of a solute that causes a temperature increment of the “solvent sublimation” enough to allowing the formation of polymeric carbon nitride to occur. Sulfate ions are presumably hosted in the rosette channels of MCA as shown by simulations. - Graphical abstract: The blend of melamine cyanurate and sulfuric acid behaves like a solution so that melamine cyanurate decomposition is shifted to temperatures high enough to react and form polymeric carbon nitride. - Highlights: • The adduct of melamine and cyanuric acid behaves as a solid solvent. • The blend of sulfuric acid and melamine cyanurate behaves like a solution. • Melamine cyanurate decomposition is shifted to higher temperatures by sulfuric acid. • The formation of polymeric carbon nitride occurs for these higher temperatures.« less

Assessment of Heat Hazard during the Polymerization of Selected Light-Sensitive Dental Materials.

PubMed

Janeczek, Maciej; Herman, Katarzyna; Fita, Katarzyna; Dudek, Krzysztof; Kowalczyk-Zając, Małgorzata; Czajczyńska-Waszkiewicz, Agnieszka; Piesiak-Pańczyszyn, Dagmara; Kosior, Piotr; Dobrzyński, Maciej

2016-01-01

Introduction. Polymerization of light-cured dental materials used for restoration of hard tooth tissue may lead to an increase in temperature that may have negative consequence for pulp vitality. Aim. The aim of this study was to determine maximum temperatures reached during the polymerization of selected dental materials, as well as the time that is needed for samples of sizes similar to those used in clinical practice to reach these temperatures. Materials and Methods. The study involved four composite restorative materials, one lining material and a dentine bonding agent. The polymerization was conducted with the use of a diode light-curing unit. The measurements of the external surface temperature of the samples were carried out using the Thermovision®550 thermal camera. Results. The examined materials significantly differed in terms of the maximum temperatures values they reached, as well as the time required for reaching the temperatures. A statistically significant positive correlation of the maximum temperature and the sample weight was observed. Conclusions. In clinical practice, it is crucial to bear in mind the risk of thermal damage involved in the application of light-cured materials. It can be reduced by using thin increments of composite materials.

Elasticity-mediated nematiclike bacterial organization in model extracellular DNA matrix.

PubMed

Smalyukh, Ivan I; Butler, John; Shrout, Joshua D; Parsek, Matthew R; Wong, Gerard C L

2008-09-01

DNA is a common extracellular matrix component of bacterial biofilms. We find that bacteria can spontaneously order in a matrix of aligned concentrated DNA, in which rod-shaped cells of Pseudomonas aeruginosa follow the orientation of extended DNA chains. The alignment of bacteria is ensured by elasticity and liquid crystalline properties of the DNA matrix. These findings show how behavior of planktonic bacteria may be modified in extracellular polymeric substances of biofilms and illustrate the potential of using complex fluids to manipulate embedded nanosized and microsized active particles.

Self-healing polymers---The importance of choosing an adequate healing monomer, and the olefin metathesis polymerization of agricultural oils

NASA Astrophysics Data System (ADS)

Mauldin, Timothy C.

Modern society's immense and ill-fated reliance on petrochemical-based polymeric materials will likely necessitate a shift in polymer production paradigms in the near future. The work presented herein attempts to address this issue via a two-pronged approach. First, efforts to improve the duration of composite materials by incorporation of a self-healing function are discussed, the fruitful application of which can potentially reduce or eliminate the massive carbon footprints associated with the repair/replacement of damaged materials. And second, polymeric materials derived predominately from natural and renewable feedstock---namely vegetable oils---are developed. Early microcapsule-based self-healing materials utilized dicyclopentadiene-filled microcapsules and Grubbs' olefin metathesis catalyst to initiate the healing mechanism. However, the patent-protected catalyst, made from the precious metal ruthenium and sometimes costly ligands, will likely never be inexpensive and therefore limit large-scale applications. Hence, clever approaches to reduce the healing catalyst loading in self-healing polymers are of great interest. To this end, our efforts have revolved around solving the problem of the relatively inefficient use of Grubbs' catalyst during the healing mechanism. Given that the mismatch of the olefin metathesis polymerization and Grubbs' catalyst dissolution (in monomer) kinetics is a known cause of this inefficient use of the catalyst, we attempted to tune the "latency" (i.e. pot life) of the olefin metathesis polymerization to ensure more complete dissolution of catalyst in monomer. In an alternative approach to improving efficient catalyst dissolution, we developed a simple model to predict relative dissolution rates of Grubbs' catalyst in a small library of healing monomers. This model was shown experimentally to be able to aid in the selection of, for example, reactive monomer additives that can yield impressive improvements in catalyst dissolution at small loadings. Furthermore, we have recently developed a novel rheokinetic technique designed to mimic the self-healing mechanism. This new analytical technique allows for collection of copious amounts of information related to the self-healing mechanism (e.g. healing kinetics, rheological and mechanical changes of polymerizing healing agents, adhesive interactions between healing agent and polymer matrix, etc.) to be extracted from a single experiment. New polymers derived from renewable feeds were synthesized via olefin metathesis polymerization techniques, which are ideally suited to react with the unactivated olefins (i.e. non-styrenic, non-acrylated, non-conjugated, etc.) prominent in most vegetable oils. Various vegetable oils were modified to contain norbornenyl functional groups via the high-pressure Diels-Alder addition of cyclopentadiene to their olefins to yield ROMP-reactive monomers. These monomers, polymerized in the presence of Grubbs' catalyst and the occasional comonomer, were able to yield highly crosslinked thermosets with ambient temperature storage moduli, glass transition temperatures and decomposition temperatures comparable to their currently-used, petrochemical-based counterparts. Other research thrusts in this area have focused on the development of renewable thermoplastic polymers. Vegetable oils were chemically modified to yield a series of alpha,o-dienes, from which polymers were formed via acyclic diene metathesis (ADMET). The resulting polymers were shown to have unique material properties, comparable to that of other biopolyesters (poly(lactic acid), poly(glycolides), poly(caprolactones), etc.) and common, petrochemical-derived polyesters.

Polymeric foams from cross-linkable poly-N-ary lenebenzimidazoles

NASA Technical Reports Server (NTRS)

Harrison, E. S.; Delano, C. B.; Riccitello, S. R. (Inventor)

1978-01-01

Foamed cross-linked poly-N-arylenebinzimidazoles are prepared by mixing an organic tetraamine and an ortho substituted aromatic dicarboxylic acid anhydride in the presence of a blowing agent, and then heating the prepolymer to a temperature sufficient to complete polymerization and foaming of the reactants. In another embodiment of the process, the reactants are heated to form a prepolymer. The prepolymer is then cured at higher temperatures to complete foaming and polymerization.

Selection of a Suitable Method for the Preparation of Polymeric Nanoparticles: Multi-Criteria Decision Making Approach

PubMed Central

Krishnamoorthy, Kannan; Mahalingam, Manikandan

2015-01-01

Purpose: The present study is aimed to select the suitable method for preparation of camptothecin loaded polymeric nanoparticles by utilizing the multi-criteria decision making method. Novel approaches of drug delivery by formulation using nanotechnology are revolutionizing the future of medicine. Recent years have witnessed unprecedented growth of research and application in the area of nanotechnology. Nanoparticles have become an important area of research in the field of drug delivery because they have the ability to deliver a wide range of drug to varying areas of body. Methods: Despite of extensive research and development, polymeric nanoparticles are frequently used to improve the therapeutic effect of drugs. A number of techniques are available for the preparation of polymeric nanoparticles. The Analytical Hierarchy Process (AHP) is a method for decision making, which are derived from individual judgements for qualitative factors, using the pair-wise comparison matrix. In AHP, a decision hierarchy is constructed with a goal, criteria and alternatives. Results: The model uses three main criteria 1) Instrument, 2) Process and Output and 3) Cost. In addition, there are eight sub-criteria’s as well as eight alternatives. Pair-wise comparison matrixes are used to obtain the overall priority weight and ranking for the selection of suitable method. Nanoprecipitation technique is the most suitable method for the preparation of camptothecin loaded polymeric nanoparticles with the highest overall priority weight of 0.297 Conclusion: In particular, the result indicates that the priority weights obtained from AHP could be defined as a multiple output for finding out the most suitable method for preparation of camptothecin loaded polymeric nanoparticles. PMID:25789220

Embedded cluster metal-polymeric micro interface and process for producing the same

DOEpatents

Menezes, Marlon E.; Birnbaum, Howard K.; Robertson, Ian M.

2002-01-29

A micro interface between a polymeric layer and a metal layer includes isolated clusters of metal partially embedded in the polymeric layer. The exposed portion of the clusters is smaller than embedded portions, so that a cross section, taken parallel to the interface, of an exposed portion of an individual cluster is smaller than a cross section, taken parallel to the interface, of an embedded portion of the individual cluster. At least half, but not all of the height of a preferred spherical cluster is embedded. The metal layer is completed by a continuous layer of metal bonded to the exposed portions of the discontinuous clusters. The micro interface is formed by heating a polymeric layer to a temperature, near its glass transition temperature, sufficient to allow penetration of the layer by metal clusters, after isolated clusters have been deposited on the layer at lower temperatures. The layer is recooled after embedding, and a continuous metal layer is deposited upon the polymeric layer to bond with the discontinuous metal clusters.

Surfactant-free, cationic latices of poly(BMA-co-MMA) using AIBA initiator.

PubMed

Lee, Ki-Chang

2013-09-01

When polymer particles come into use, especially, for photonic crystal applications, their diameter, dispersivity, and refractive indices become very important. Poly(benzyl methacrylate) is known to be a kind of high refracive materials (n = 1.57) compared to poly(methyl methacrylate) (n = 1.49). Not many work was concerned for surfactant-free emulsion polymerization of benzyl methacrylate or its copolymerization using cationic initiators. Narrowly dispersed cationic poly(BMA-co-MMA) and PBMA latices were synthesized successfully by surfactant-free emulsion polymerization with AIBA. The influences of BMA/MMA ratio, BMA/MMA monomer and initiator concentrations, addition of DVB/EGDMA crosslink agent, and polymerization temperature on the kinetics and on the particle size and molecular weight were studied. Monodisperse cationic charged PBMA and poly(BMA-coMMA) latices with particle diameters varying between 160-494 nm and polymer molecular weights of the order 1.25 x 10(4) to 7.55 x 10(4) g/mol were prepared. The rate of polymerization increased with increasing MMA concentration in BMA/MMA ratio, AIBA concentration, DVB crosslink agent, and polymerization temperature. The particle diameter increased with BMA concentration in BMA/MMA ratio, AIBA concentration, and BMA/MMA monomer concentration. The molecular weight increased with BMA concentration in BMA/MMA ratio and BMA/MMA monomer concentration. The glass transition temperature of the latex copolymers decreased with increasing amount of BMA from 375 K for PMMA to 321 K for PBMA. It was, thus, found that the particle diameter and rate of polymerization as well as the polymer molecular weight for surfactant-free emulsion polymerization of BMA and MMA can be controlled easily by controlling the BMA/MMA ratio, BMA/MMA monomer concentration, AIBA concentration, and polymerization temperature.

L-Lactide Ring-Opening Polymerization with Tris(acetylacetonate)Titanium(IV) for Renewable Material.

PubMed

Kim, Da Hee; Yoo, Ji Yun; Ko, Young Soo

2016-05-01

A new Ti-type of catalyst for L-lactide polymerization was synthesized by reaction of titanium(IV) isopropoxide (TTIP) with acetylacetone (AA). Moreover, PLA was prepared by the bulk ring-opening polymerization using synthesized Ti catalyst. Polymerization behaviors were examined depending on monomer/catalyst molar ratio, polymerization temperature and time. The structure of synthesized catalysts was verified with FT-IR and 1H NMR and the properties of poly(L-lactide) (PLLA) were examined by GPC, DSC and FT-IR. There existed about 30 minutes of induction time at the monomer/catalyst molar ratio of 300. The molecular weight (MW) increased as monomer/catalyst molar ratio increased. The MW increased almost linearly as polymerization progressed. Increasing polymerization temperature increased the molecular weight of PLLA as well as monomer/catalyst molar ratio. The melting point (T(m)) of polymers was in the range of 142 to 167 degrees C. Lower T(m) was expected to be resulted from relatively lower molecular weight.

Effects of physical aging on long-term creep of polymers and polymer matrix composites

NASA Technical Reports Server (NTRS)

Brinson, L. Catherine; Gates, Thomas S.

1994-01-01

For many polymeric materials in use below the glass transition temperature, the long term viscoelastic behavior is greatly affected by physical aging. To use polymer matrix composites as critical structural components in existing and novel technological applications, this long term behavior of the material system must be understood. Towards that end, this study applied the concepts governing the mechanics of physical aging in a consistent manner to the study of laminated composite systems. Even in fiber-dominated lay-ups the effects of physical aging are found to be important in the long-term behavior of the composite. The basic concepts describing physical aging of polymers are discussed. Several aspects of physical aging which have not been previously documented are also explored in this study, namely the effects of aging into equilibrium and a relationship to the time-temperature shift factor. The physical aging theory is then extended to develop the long-term compliance/modulus of a single lamina with varying fiber orientation. The latter is then built into classical lamination theory to predict long-time response of general oriented lamina and laminates. It is illustrated that the long term response can be counterintuitive, stressing the need for consistent modeling efforts to make long term predictions of laminates to be used in structural situations.

Experiments of the Essential Amino Acids at high temperature and high pressure using DAC

NASA Astrophysics Data System (ADS)

Kubo, K.; Okamoto, K.

2017-12-01

Amino acids are organic compounds that form the fundamental part of life. Proteins are formed by peptide binding and polymerization of amino acids. Amino acids are polymerized in the ridge hydrothermal field, formed proteins, and might be evolved into life. Experimental studies on the polymerization of amino acids in hydrothermal environments have been conducted. However, they were hydrothermal experiments and after the experiments. All run products (amid-acids) were observed at ambient condition. Few in-situ observations of amino acids were done in experiments in hydrothermal condition. In order to perform in-situ observation of the polymerization of amino acids, we have conducted the DAC experiments. Amino acids were filled in the DAC, pressures were applied, then heated to high temperature with Raman analysis. In preliminary experiment using glycine, polymerization forming diglycine, were completed. Investigation amino acids polymerization under hydrothermal condition would shed light for new view of early life science.

In Situ Thermal Generation of Silver Nanoparticles in 3D Printed Polymeric Structures

PubMed Central

Fantino, Erika; Chiappone, Annalisa; Calignano, Flaviana; Fontana, Marco; Pirri, Fabrizio; Roppolo, Ignazio

2016-01-01

Polymer nanocomposites have always attracted the interest of researchers and industry because of their potential combination of properties from both the nanofillers and the hosting matrix. Gathering nanomaterials and 3D printing could offer clear advantages and numerous new opportunities in several application fields. Embedding nanofillers in a polymeric matrix could improve the final material properties but usually the printing process gets more difficult. Considering this drawback, in this paper we propose a method to obtain polymer nanocomposites by in situ generation of nanoparticles after the printing process. 3D structures were fabricated through a Digital Light Processing (DLP) system by disolving metal salts in the starting liquid formulation. The 3D fabrication is followed by a thermal treatment in order to induce in situ generation of metal nanoparticles (NPs) in the polymer matrix. Comprehensive studies were systematically performed on the thermo-mechanical characteristics, morphology and electrical properties of the 3D printed nanocomposites. PMID:28773716

The Importance of Interactions at the Molecular Level: A Spectroscopic Study of a New Composite Sorber Material.

PubMed

Crocellà, Valentina; Groppo, Elena; Dani, Alessandro; Castellero, Alberto; Bordiga, Silvia; Zilio, Stefano; De Simone, Agnello; Vacca, Paolo

2017-10-01

The functional properties of a new composite material having water vapor getter properties have been investigated by a large arsenal of characterization techniques. The composite system is originated by combining two constituents having very different chemical natures, a magnesium perchlorate (Mg(ClO 4 ) 2 ) salt and a polymeric acrylic matrix. In particular, Fourier transform infrared (FT-IR) and Raman spectroscopy have been fundamental to understand the type of interactions between the salt and the matrix in different hydration conditions. It was found that in the anhydrous composite system the dispersed Mg(ClO 4 ) 2 salt retains its molecular structure, because Mg 2+ cations are still surrounded by their [ClO 4 ] - counter-anions; at the same time, the salt and the polymeric matrix chemically interact each other at the molecular level. These interactions gradually vanish in the presence of water, and disappear in the fully hydrated composite system, where the Mg 2+ cations are completely solvated by the water molecules.

Relationship between Eu{sup 3+} reduction and glass polymeric structure in Al{sub 2}O{sub 3}-modified borate glasses under air atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiao, Qing; Yu, Xue; Xu, Xuhui

2013-06-15

The reduction of Eu{sup 3+} to Eu{sup 2+} is realized efficiently in Eu{sub 2}O{sub 3}-doped borate glasses prepared under air condition by melting-quenching method. Luminescent spectra show an increasing tendency of Eu{sup 2+} emission with increasing Al{sub 2}O{sub 3} concentration in B{sub 2}O{sub 3}–Na{sub 2}O glasses. It is interesting that significant enhancement appeared of Eu{sup 2+} luminescence in the Al{sub 2}O{sub 3}-rich sample comparing to the samples of Al{sub 2}O{sub 3} less than 6 mol%. FTIR and Raman scattering measurements indicated that some new vibration modes assigned to the low-polymerized structure groups decomposed from the slight Al{sub 2}O{sub 3} dopantmore » samples. These results demonstrated that the polymerization of the glass structure decreased with increasing incorporation of Al{sub 2}O{sub 3} into the borate glasses, linking to the efficiency of Eu{sup 3+} self-reduction in air at high temperature. - graphical abstract: A novel europium valence reduction phenomenon occurred in Al{sub 2}O{sub 3} modified borate glasses, FTIR and Raman measurements revealed that high polymeric groups were destroyed to low polymery structures with Al{sub 2}O{sub 3} addition. - Highlights: • The efficient reduction of Eu{sup 3+} to Eu{sup 2+} is observed in the B{sub 2}O{sub 3}–Na{sub 2}O glasses. • Eu{sup 2+} luminescence is significant enhanced in the Al{sub 2}O{sub 3}-rich glasses. • The introduction of Al{sub 2}O{sub 3} changed the network structure of the borate glasses. • High polymeric borate groups in the glass matrix may be destroyed to the lower ones.« less

The origin of life in geothermal hot springs: Darwin's warm little pond revisited

NASA Astrophysics Data System (ADS)

Deamer, D.

2016-12-01

The origin of life in geothermal hot springs: Darwin's warm little pond revisited David Deamer and Bruce Damer, Department of Biomolecular Engineering, University of California, Santa Cruz CA 95064 We are exploring ways in which mononucleotides can undergo polymerization and encapsulation in the presence of an organizing matrix (1, 2, 3). When mixtures of amphiphilic lipids and mononucleotides are exposed to cycles of dehydration and rehydration, the lipids concentrate and organize the monomers within multilamellar liquid-crystalline matrices that self-assemble in the dry state. The chemical potential driving the polymerization reaction is supplied by the anhydrous conditions in which water becomes a leaving group, with heat providing activation energy. Upon rehydration, the polymeric products are encapsulated in trillions of microscopic compartments. Each compartment is unique in its composition and contents, and can be considered to be an experiment in a natural version of combinatorial chemistry that would be ubiquitous in the prebiotic environment. There are specific thermodynamic and kinetic considerations required for this process to work which are related to cycles of evaporation and rehydration, ionic composition, salt concentration, pH and temperature. These conditions are present in hydrothermal fields associated with volcanic activity on today's Earth and can be compared with the range of possible conditions on Enceladus to estimate the probability that life can emerge on an icy world with a subsurface salty liquid ocean. 1. De Guzman V, Shenasa H, Vercoutere W, Deamer D (2014) Generation of oligonucleotides under hydrothermal conditions by non-enzymatic polymerization. J Mol Evol 78:251-262 2. Deamer D. 2012. Liquid crystalline nanostructures: organizing matrices for non-enzymatic nucleic acid polymerization. Chem Soc Rev. 41:5375-9. 3. Damer B, Deamer D. 2015. Coupled phases and combinatorial selection in fluctuating hydrothermal pools: a scenario to guide experimental approaches to the origin of cellular life. Life 5:872-87.

Novel biomimetic composite material for potentiometric screening of acetylcholine, a neurotransmitter in Alzheimer's disease.

PubMed

Sacramento, Ana S; Moreira, Felismina T C; Guerreiro, Joana L; Tavares, Ana P; Sales, M Goreti F

2017-10-01

This work describes a novel approach to produce an antibody-like biomimetic material. It includes preparing composite imprinted material never presented before, with highly conductive support nanostructures and assembling a high conductivity polymeric layer at low temperature. Overall, such highly conductive material may enhance the final features of electrically-based devices. Acetylcholine (ACh) was selected as target analyte, a neurotransmitter of importance in Alzheimer's disease. Potentiometric transduction was preferred, allowing quick responses and future adaptation to point-of-care requirements. The biomimetic material was obtained by bulk polymerization, where ACh was placed in a composite matrix of multiwalled carbon nanotubes (MWCNTs) and aniline (ANI). Subsequent polymerization, initiated by radical species, yielded a polymeric structure of polyaniline (PANI) acting as physical support of the composite. A non-imprinted material (NIM) having only PANI/MWCNT (without ACh) has been prepared for comparison of the biomimetic-imprinted material (BIM). RAMAN and Fourier Transform Infrared spectroscopy (FTIR), Transmission Electron microscopy (TEM), and Scanning Electron microscope (SEM) analysis characterized the structures of the materials. The ability of this biomaterial to rebind ACh was confirmed by including it as electroactive compound in a PVC/plasticizer mixture. The membranes with imprinted material and anionic additive presented the best analytical characteristics, with a sensitivity of 83.86mV decade -1 and limit of detection (LOD) of 3.45×10 -5 mol/L in HEPES buffer pH4.0. Good selectivity was observed against creatinine, creatine, glucose, cysteine and urea. The electrodes were also applied on synthetic serum samples and seemed a reliable tool for screening ACh in synthetic serum samples. The overall performance showed fast response, reusability, simplicity and low price. Copyright © 2017 Elsevier B.V. All rights reserved.

Hierarchical self-assembly: Self-organized nanostructures in a nematically ordered matrix of self-assembled polymeric chains

NASA Astrophysics Data System (ADS)

Mubeena, Shaikh; Chatterji, Apratim

2015-03-01

We report many different nanostructures which are formed when model nanoparticles of different sizes (diameter σn) are allowed to aggregate in a background matrix of semiflexible self-assembled polymeric wormlike micellar chains. The different nanostructures are formed by the dynamical arrest of phase-separating mixtures of micellar monomers and nanoparticles. The different morphologies obtained are the result of an interplay of the available free volume, the elastic energy of deformation of polymers, the density (chemical potential) of the nanoparticles in the polymer matrix, and, of course, the ratio of the size of self-assembling nanoparticles and self-avoidance diameter of polymeric chains. We have used a hybrid semi-grand-canonical Monte Carlo simulation scheme to obtain the (nonequilibrium) phase diagram of the self-assembled nanostructures. We observe rodlike structures of nanoparticles which get self-assembled in the gaps between the nematically ordered chains, as well as percolating gel-like network of conjoined nanotubes. We also find a totally unexpected interlocked crystalline phase of nanoparticles and monomers, in which each crystal plane of nanoparticles is separated by planes of perfectly organized polymer chains. We identified the condition which leads to such interlocked crystal structure. We suggest experimental possibilities of how the results presented in this paper could be used to obtain different nanostructures in the laboratory.

Preparation of monomeric and polymeric β-cyclodextrin functionalized monoliths for rapid isolation and purification of puerarin from Radix puerariae.

PubMed

Lv, Yongqin; Hughes, Timothy C; Hao, Xiaojuan; Mei, Danping; Tan, Tianwei

2011-08-01

Monomeric and epichlorohydrin polymerized β-CD functionalized monoliths were prepared for the rapid isolation and purification of the isoflavonoid puerarin, a well-known traditional Chinese drug, from a crude extract of Radix puerariae (root of the plant Pueraria lobata). Two copolymers poly(isocyanatoethyl methacrylate-co-methyl methacrylate-co-ethylene dimethacrylate) (poly(IEM-co-MMA-co-EDMA)) and poly(glycidyl methacrylate-co-EDMA) (poly(GMA-co-EDMA)) were developed as facile, highly reactive and versatile monolithic matrix. SEM characterization demonstrated that the modified monoliths had homogenous porous structure and morphology. The success of the chemical modification of the monolithic matrix was confirmed by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), solid-state (13) C NMR and elemental analysis. It was demonstrated that polymeric β-CD modified monoliths had better separation and selectivity for puerarin, recovering puerarin with a purity of 96% (m%) and a yield of 93% (m%). Compared with poly(glycidyl methacrylate-co-EDMA), poly(isocyanatoethyl methacrylate-co-methyl methacrylate-co-EDMA) monolithic matrix had higher reactivity, which significantly improved the β-CD ligand density and thus the selectivity of the monoliths. Puerarin with a purity of 96% (m%) and with a yield of 89% (m%) was recovered on the monolith. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Complexity in modeling of residual stresses and strains during polymerization of bone cement: effects of conversion, constraint, heat transfer, and viscoelastic property changes.

PubMed

Gilbert, Jeremy L

2006-12-15

Aseptic loosening of cemented joint prostheses remains a significant concern in orthopedic biomaterials. One possible contributor to cement loosening is the development of porosity, residual stresses, and local fracture of the cement that may arise from the in-situ polymerization of the cement. In-situ polymerization of acrylic bone cement is a complex set of interacting processes that involve polymerization reactions, heat generation and transfer, full or partial mechanical constraint, evolution of conversion- and temperature-dependent viscoelastic material properties, and thermal and conversion-driven changes in the density of the cement. Interactions between heat transfer and polymerization can lead to polymerization fronts moving through the material. Density changes during polymerization can, in the presence of mechanical constraint, lead to the development of locally high residual strain energy and residual stresses. This study models the interactions during bone cement polymerization and determines how residual stresses develop in cement and incorporates temperature and conversion-dependent viscoelastic behavior. The results show that the presence of polymerization fronts in bone cement result in locally high residual strain energies. A novel heredity integral approach is presented to track residual stresses incorporating conversion and temperature dependent material property changes. Finally, the relative contribution of thermal- and conversion-dependent strains to residual stresses is evaluated and it is found that the conversion-based strains are the major contributor to the overall behavior. This framework provides the basis for understanding the complex development of residual stresses and can be used as the basis for developing more complex models of cement behavior.

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

NASA Astrophysics Data System (ADS)

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.

Hydrogel-Based Fluorescent Dual pH and Oxygen Sensors Loaded in 96-Well Plates for High-Throughput Cell Metabolism Studies.

PubMed

Wu, Shanshan; Wu, Siying; Yi, Zheyuan; Zeng, Fei; Wu, Weizhen; Qiao, Yuan; Zhao, Xingzhong; Cheng, Xing; Tian, Yanqing

2018-02-13

In this study, we developed fluorescent dual pH and oxygen sensors loaded in multi-well plates for in-situ and high-throughput monitoring of oxygen respiration and extracellular acidification during microbial cell growth for understanding metabolism. Biocompatible PHEMA-co-PAM materials were used as the hydrogel matrix. A polymerizable oxygen probe (OS2) derived from PtTFPP and a polymerizable pH probe (S2) derived from fluorescein were chemically conjugated into the matrix to solve the problem of the probe leaching from the matrix. Gels were allowed to cure directly on the bottom of 96-well plates at room-temperature via redox polymerization. The influence of matrix's composition on the sensing behaviors was investigated to optimize hydrogels with enough robustness for repeatable use with good sensitivity. Responses of the dual sensing hydrogels to dissolved oxygen (DO) and pH were studied. These dual oxygen-pH sensing plates were successfully used for microbial cell-based screening assays, which are based on the measurement of fluorescence intensity changes induced by cellular oxygen consumption and pH changes during microbial growth. This method may provide a real-time monitoring of cellular respiration, acidification, and a rapid kinetic assessment of multiple samples for cell viability as well as high-throughput drug screening. All of these assays can be carried out by a conventional plate reader.

Apple cuticle: the perfect interface

NASA Astrophysics Data System (ADS)

Curry, Eric; Arey, Bruce

2010-06-01

The domestic apple might well be called an 'extreme' fruit. In the arid Northwest United States, the fruit often tolerates surface temperatures ranging from -2 °C in the early spring to 50 °C in the heat of summer, and again to -2 °C during controlled postharvest storage for up to 12 months. During its 18-month existence, the apple maintains a cuticle that is dynamic and environmentally responsive to protect against 1) cellular water loss during desiccation stress and 2) excessive uptake of standing surface moisture. Physiological disorders of the peel such as russeting, cracking, splitting, flecking and lenticel marking, develop as epidermal cells respond to rapid changes in ambient conditions at specific developmental stages during the growing season. Resultant market losses underlie research investigating the nature of apple cuticle growth and development. Ultrastructural analysis of the pro-cuticle using scanning electron microscopy indicates an overlapping network of lipid-based distally-elongating microtubules--produced by and connected to epidermal cells--which co-polymerize to form an organic solvent-insoluble semi-permeable cutin matrix. Microtubule elongation, aggregation, and polymerization function together as long as the fruit continues to enlarge. The nature of lipid transport from the epidermal cells through the cell wall to become part of the cuticular matrix was explored using an FEI Helios NanoLabTM DualBeamTM focused ion beam/scanning electron microscope on chemically- and cryo-fixed peel tissue from mature or freshly harvested apples. Based on microtubule dimensions, regular projections found at the cell/cuticle interface suggest an array of microtubule-like structures associated with the epidermal cell.

Organic/Inorganic Polymeric Composites for Heat-Transfer Reduction

NASA Technical Reports Server (NTRS)

Smith, Trent; Williams, Martha

2008-01-01

Organic/inorganic polymeric composite materials have been invented with significant reduction in heat-transfer properties. Measured decreases of 20-50 percent in thermal conductivity versus that of the unmodified polymer matrix have been attained. These novel composite materials also maintain mechanical properties of the unmodified polymer matrix. The present embodiments are applicable, but not limited to: racing applications, aerospace applications, textile industry, electronic applications, military hardware improvements, and even food service industries. One specific application of the polymeric composition is for use in tanks, pipes, valves, structural supports, and components for hot or cold fluid process systems where heat flow through materials is problematic and not desired. With respect to thermal conductivity and physical properties, these materials are superior alternatives to prior composite materials. These materials may prove useful as substitutes for metals in some cryogenic applications. A material of this type can be made from a blend of thermoplastics, elastomers, and appropriate additives and processed on normal polymer processing equipment. The resulting processed organic/inorganic composite can be made into fibers, molded, or otherwise processed into useable articles.

LED Curing Lights and Temperature Changes in Different Tooth Sites

PubMed Central

Armellin, E.; Bovesecchi, G.; Coppa, P.; Pasquantonio, G.; Cerroni, L.

2016-01-01

Objectives. The aim of this in vitro study was to assess thermal changes on tooth tissues during light exposure using two different LED curing units. The hypothesis was that no temperature increase could be detected within the dental pulp during polymerization irrespective of the use of a composite resin or a light-curing unit. Methods. Caries-free human first molars were selected, pulp residues were removed after root resection, and four calibrated type-J thermocouples were positioned. Two LED lamps were tested; temperature measurements were made on intact teeth and on the same tooth during curing of composite restorations. The data was analyzed by one-way analysis of variance (ANOVA), Wilcoxon test, Kruskal-Wallis test, and Pearson's χ 2. After ANOVA, the Bonferroni multiple comparison test was performed. Results. Polymerization data analysis showed that in the pulp chamber temperature increase was higher than that without resin. Starlight PRO, in the same condition of Valo lamp, showed a lower temperature increase in pre- and intrapolymerization. A control group (without composite resin) was evaluated. Significance. Temperature increase during resin curing is a function of the rate of polymerization, due to the exothermic polymerization reaction, the energy from the light unit, and time of exposure. PMID:27195282

LED Curing Lights and Temperature Changes in Different Tooth Sites.

PubMed

Armellin, E; Bovesecchi, G; Coppa, P; Pasquantonio, G; Cerroni, L

2016-01-01

Objectives. The aim of this in vitro study was to assess thermal changes on tooth tissues during light exposure using two different LED curing units. The hypothesis was that no temperature increase could be detected within the dental pulp during polymerization irrespective of the use of a composite resin or a light-curing unit. Methods. Caries-free human first molars were selected, pulp residues were removed after root resection, and four calibrated type-J thermocouples were positioned. Two LED lamps were tested; temperature measurements were made on intact teeth and on the same tooth during curing of composite restorations. The data was analyzed by one-way analysis of variance (ANOVA), Wilcoxon test, Kruskal-Wallis test, and Pearson's χ (2). After ANOVA, the Bonferroni multiple comparison test was performed. Results. Polymerization data analysis showed that in the pulp chamber temperature increase was higher than that without resin. Starlight PRO, in the same condition of Valo lamp, showed a lower temperature increase in pre- and intrapolymerization. A control group (without composite resin) was evaluated. Significance. Temperature increase during resin curing is a function of the rate of polymerization, due to the exothermic polymerization reaction, the energy from the light unit, and time of exposure.

The energetics of adhesion in composite materials

NASA Astrophysics Data System (ADS)

Harding, Philip Hiram

Composite materials are used throughout modern society, and often the most important parameter in determining their properties is the adhesion at material interfaces within the composite. A broad investigation is completed, the global objective of which is to develop understanding of the role of adhesion in composite materials. The scope of this study ranges from macroscopic effects of adhesion on filled polymer composites to microscopic adhesion measurements with engineered interfaces. The surface of a filler material is systematically modified and surface characterization techniques are used to quantify the influence of the surface treatments on surface energetics and wetting properties. Filled polymer composites are prepared and composite mechanical properties determined with beam deflection tests. Filler surface treatments significantly alter the composite yield stress for composites which fail interfacially and are observed to increase or decrease mechanical strength, depending on the chemical nature of the modification. Thermodynamic adhesion mechanisms active at the filler-matrix interfaces are then explored by making direct interfacial strength measurements whereby a single spherical particle is introduced into the polymeric matrix. Interfacial strength is determined by submitting the single-particle composite (SPC) to uni-axial tension and relating the macroscopic stress at interfacial failure to that experienced at the interface. The technique provides a measurement of interfacial strength between two elastic materials, one unaffected by frictional forces, viscoelasticity, and thermal stresses. The SPC measurements are used to verify proposed adhesion mechanisms at the various filler-polymer interfaces and establish the role of adhesion in the filled polymer composites. The SPC technique is then used to investigate the adhesion promotion mechanism of organofunctional silanes, which are shown to be controlled by the compatibility and penetration of the silane organofunctional group. The effects of thermal residual stresses on interfacial strength are also investigated using the SPC technique. Processing conditions, i.e., time-temperature profiles, are used to systematically vary the thermal residual stresses within the polymeric matrix. The interfaces studied are deleteriously affected by increases in thermal residual stresses.

In-port derivatization coupled to different extraction techniques for the determination of alkylphenols in environmental water samples.

PubMed

Cavalheiro, J; Monperrus, M; Amouroux, D; Preud'Homme, H; Prieto, A; Zuloaga, O

2014-05-02

Large volume injection (LVI)-in port silylation coupled to gas chromatography-mass spectrometry (GC-MS) for the determination of alkylphenols (APs) in water samples applying four different extraction approaches was evaluated. Among the variables studied for in-port derivatization, vent time, cryo-focusing temperature and the ratio solvent volume/N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) volume were optimized using an experimental design approach. Regarding the extraction techniques, different approaches previously optimized in the research group were tested. On the one hand different polymeric materials were tested: silicon rod (SR), polyethersulfone (PES) and polydimethylsiloxane (PDMS), the latter in the stir-bar sorptive extraction format (SBSE-PDMS). PES was chosen among the polymeric materials due to the higher recoveries (compared with SR) and lower price (compared to PDMS in the stir-bar sorptive extraction, SBSE-PDMS). Both MASE and PES protocols were selected at this point for further method validation and application to real samples. Finally, the developed methods were validated and applied to the determination of target analytes in various aqueous environmental matrices, including estuarine water and wastewater. Acceptable repeatability in the case of MASE (5-17%) and PES (7-21%) procedures and method detection limits (MDLs, 5-123 and 28-328 ng L(-1) for PES and MASE, respectively) were obtained for most analytes. In terms of apparent recoveries in the presence of matrix, estuarine and effluent samples showed no significant matrix effect (apparent recoveries in the 73-121% for PES and 74-128% for MASE), while a stronger matrix effect was observed for influent wastewater samples (98-132% for PES and 65-156% for MASE). Both MASE and PES extractions combined with LVI-in-port derivatization-GC-MS were applied to the determination of APs in the estuary of Bilbao (Gulf of Biscay, Spain). Copyright © 2014 Elsevier B.V. All rights reserved.

Fabrication of Graphene Oxide/Polypropylene Nanocomposites and Their Electrical Conductivity Study

NASA Astrophysics Data System (ADS)

Dong, Jinyong

2011-03-01

Graphene oxide (GO) /polypropylene nanocomposites were fabricated via in situ polymerizing propylene monomer over a GO that had been treated with a Grignard reagent and TiCl 4 successively when GO was not only catalytically activated but also largely reduced to an almost O- free state. The polymerization led to the in situ formation of the PP matrix, which was synchronized by the nanoscale exfoliation of the reduced GO as well as its gradual dispersion. Morphological examination of the ultimate GO/PP nanocomposites by TEM and SEM techniques revealed effective dispersion in nanoscale of GO in PP matrix. High electrical conductivity was discovered with thus prepared GO/PP nanocomposites, e.g. at a GO loading of 4.9 wt%, σc was measured at 0.3 S . m -1

Enhanced performance of biodegradable poly(butylene succinate)/graphene oxide nanocomposites via in situ polymerization.

PubMed

Wang, X W; Zhang, C-A; Wang, P L; Zhao, J; Zhang, W; Ji, J H; Hua, K; Zhou, J; Yang, X B; Li, X P

2012-05-08

Poly(butylene succinate) (PBS)/graphene oxide (GO) nanocomposites were facilely prepared via in situ polymerization. The properties of the nanocomposites were studied using FTIR, XRD, and (1)H NMR, and the state of dispersion of GO in the PBS matrix was examined by SEM. The crystallization and melting behavior of the PBS matrix in the presence of dispersed GO nanosheets have been studied by DSC and polarized optical microscopy. Through the mechnical testing machine and DMA, PBS/GO nanocomposites with 3% GO have shown a 43% increase in tensile strength and a 45% improvement in storage modulus. This high performance of the nanocomposites is mainly attributed to the high strength of graphene oxide combined with the strong interfacial interactions in the uniformly dispersed PBS/GO nanocomposites.

Supramolecular gelation of a polymeric prodrug for its encapsulation and sustained release.

PubMed

Ma, Dong; Zhang, Li-Ming

2011-09-12

A polymeric prodrug, PEGylated indomethacin (MPEG-indo), was prepared and then used to interact with α-cyclodextrin (α-CD) in their aqueous mixed system. This process could lead to the formation of supramolecular hydrogel under mild conditions and simultaneous encapsulation of MPEG-indo in the hydrogel matrix. For the formed supramolecular hydrogel, its gelation kinetics, mechanical strength, shear-thinning behavior and thixotropic response were investigated with respect to the effects of MPEG-indo and α-CD amounts by dynamic and steady rheological tests. Meanwhile, the possibility of using this hydrogel matrix as injectable drug delivery system was also explored. By in vitro release and cell viability tests, it was found that the encapsulated MPEG-indo could exhibit a controlled and sustained release behavior as well as maintain its biological activity.

Evaluation of shrinkage polymerization and temperature of different acrylic resins used to splinting transfer copings in indirect impression technique

NASA Astrophysics Data System (ADS)

Franco, Ana Paula G. O.; Karam, Leandro Z.; Galvão, José R.; Kalinowski, Hypolito J.

2015-09-01

The aim of the present study was evaluate the shrinkage polymerization and temperature of different acrylic resins used to splinting transfer copings in indirect impression technique. Two implants were placed in an artificial bone, with the two transfer copings joined with dental floss and acrylic resins; two dental resins are used. Measurements of deformation and temperature were performed with Fiber Braggs grating sensor for 17 minutes. The results revealed that one type of resin shows greater values of polymerization shrinkage than the other. Pattern resins did not present lower values of shrinkage, as usually reported by the manufacturer.

Liquid-Solid Self-Lubricated Coatings

NASA Astrophysics Data System (ADS)

Armada, S.; Schmid, R.; Equey, S.; Fagoaga, I.; Espallargas, N.

2013-02-01

Self-lubricated coatings have been a major topic of interest in thermal spray in the last decades. Self-lubricated coatings obtained by thermal spray are exclusively based on solid lubricants (PTFE, h-BN, graphite, MoS2, etc.) embedded in the matrix. Production of thermal spray coatings containing liquid lubricants has not yet been achieved because of the complexity of keeping a liquid in a solid matrix during the spraying process. In the present article, the first liquid-solid self-lubricating thermal spray coatings are presented. The coatings are produced by inserting lubricant-filled capsules inside a polymeric matrix. The goal of the coating is to release lubricant to the system when needed. The first produced coatings consisted solely of capsules for confirming the feasibility of the process. For obtaining such a coating, the liquid-filled capsules were injected in the thermal spray flame without any other feedstock material. Once the concept and the idea were proven, a polymer was co-sprayed together with the capsules to obtain a coating containing the lubricant-filled capsules distributed in the solid polymeric matrix. The coatings and the self-lubricated properties have been investigated by means of optical microscopy, Scanning Electron Microscopy, and tribological tests.

Health monitoring method for composite materials

DOEpatents

Watkins, Jr., Kenneth S.; Morris, Shelby J [Hampton, VA

2011-04-12

An in-situ method for monitoring the health of a composite component utilizes a condition sensor made of electrically conductive particles dispersed in a polymeric matrix. The sensor is bonded or otherwise formed on the matrix surface of the composite material. Age-related shrinkage of the sensor matrix results in a decrease in the resistivity of the condition sensor. Correlation of measured sensor resistivity with data from aged specimens allows indirect determination of mechanical damage and remaining age of the composite component.

Poly(n-hexyl methacrylate) polymerization in three-component microemulsion stabilized by a cationic surfactant.

PubMed

Katime, Issa; Arellano, Jesús; Schulz, Pablo

2006-04-15

The polymerization of n-hexyl methacrylate (n-HMA) in three-component microemulsion stabilized with dodecyltrimethylammonium bromide (DTAB) is reported as a function of monomer and initiator concentrations and temperature. The obtained latices were bluish, transparent, and translucent. Particle sizes and molar masses were on the order of 20 nm and 3 x 10(6) g/mol, respectively. In all cases, high reaction rates and final conversions of 98% were obtained. Polymerization temperature has a strong effect on reaction rate and conversion.

Synthesis and properties of hemicelluloses-based semi-IPN hydrogels.

PubMed

Peng, Feng; Guan, Ying; Zhang, Bing; Bian, Jing; Ren, Jun-Li; Yao, Chun-Li; Sun, Run-Cang

2014-04-01

Hemicelluloses were extracted from holocellulose of bamboo by alkaline treatment. The phosphorylated poly(vinyl alcohol) (P-PVA) samples with various substitution degrees were prepared through the esterification of PVA and phosphoric acid. A series of hydrogels of semi-interpenetrating polymeric networks (semi-IPN) composed of hemicelluloses-g-poly(acrylic acid) (HM-g-PAA) and the phosphorylated poly(vinyl alcohol) (P-PVA) were prepared by radical polymerization using potassium persulphate (KPS) as initiator. The HM-g-PAA networks were crosslinked by N,N-methylenebisacrylamide (MBA) as a crosslinking agent in the presence of linear P-PVA. FT-IR results confirmed that the hydrogels comprised a porous crosslink structure of P-PVA and HM with side chains that carried carboxylate and phosphorylate groups. SEM observations indicated that the incorporation of P-PVA induced highly porous structure, and P-PVA was uniformly dispersed in the polymeric network. The interior network structures of the semi-IPN matrix became more porous with increasing P-PVA. The TGA results showed that the thermo-decomposing temperature and thermal stability were increased effectively for intruding the chain of P-PVA. The maximum equilibrium swelling ratio of hydrogels in distilled water and 0.9 wt% sodium chloride solutions was up to 1085 g g(-1) and 87 g g(-1), respectively. The compressive strength increased with increasing the MBA/HM and P-PVA/HM ratios, and decreased with the increment of AA/HM ratio. Copyright © 2014 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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.

Reinforcement effect of poly(butylene succinate) (PBS)-grafted cellulose nanocrystal on toughened PBS/polylactic acid blends.

PubMed

Zhang, Xuzhen; Zhang, Yong

2016-04-20

Poly(butylene succinate) (PBS)/polylactic acid (PLA) blends modified with dicumyl peroxide (DCP) were reinforced by PBS-g-cellulose nanocrystal (CNC) through melt mixing. PBS-g-CNC was prepared through in situ polymerization and its structure was confirmed by FTIR, (13)C NMR, XPS and GPC analysis after saponification. The morphological analysis of PBS/PLA/PBS-g-CNC composites before and after etched by CH2Cl2 shows that the addition of DCP and PBS-g-CNC could decrease the size of PBS as a dispersed phase in PLA matrix and improve the dispersion of PBS-g-CNC in both PBS and PLA phases, which could affect the crystallization and mechanical properties of composites. The crystallinity of PLA α'-phase crystal in PBS/PLA/PBS-g-CNC composites is increased obviously by the addition of PBS-g-CNC, leading to an increase of the crystallinity of the composites. PBS/PLA blends modified by DCP have high Notched Izod impact strength and moduli, and the values are increased by the addition of PBS-g-CNC. Both storage modulus and glass translation temperature of PBS/PLA blend are increased by DCP and PBS-g-CNC, which is proved by DMA results, showing a weak molecular segment mobility of PBS/PLA matrix. The addition of DCP decreases the crystallization temperature and crystallinity of PBS/PLA composite, but increases the thermal stability of composites, mostly because of the crosslink effect of DCP on PBS/PLA matrix. Copyright © 2015 Elsevier Ltd. All rights reserved.

Tunable Collagen I Hydrogels for Engineered Physiological Tissue Micro-Environments

PubMed Central

Antoine, Elizabeth E.; Vlachos, Pavlos P.; Rylander, Marissa N.

2015-01-01

Collagen I hydrogels are commonly used to mimic the extracellular matrix (ECM) for tissue engineering applications. However, the ability to design collagen I hydrogels similar to the properties of physiological tissues has been elusive. This is primarily due to the lack of quantitative correlations between multiple fabrication parameters and resulting material properties. This study aims to enable informed design and fabrication of collagen hydrogels in order to reliably and reproducibly mimic a variety of soft tissues. We developed empirical predictive models relating fabrication parameters with material and transport properties. These models were obtained through extensive experimental characterization of these properties, which include compression modulus, pore and fiber diameter, and diffusivity. Fabrication parameters were varied within biologically relevant ranges and included collagen concentration, polymerization pH, and polymerization temperature. The data obtained from this study elucidates previously unknown fabrication-property relationships, while the resulting equations facilitate informed a priori design of collagen hydrogels with prescribed properties. By enabling hydrogel fabrication by design, this study has the potential to greatly enhance the utility and relevance of collagen hydrogels in order to develop physiological tissue microenvironments for a wide range of tissue engineering applications. PMID:25822731

A Comparison of Tension and Compression Creep in a Polymeric Composite and the Effects of Physical Aging on Creep Behavior

NASA Technical Reports Server (NTRS)

Gates, Thomas S.; Veazie, David R.; Brinson, L. Catherine

1996-01-01

Experimental and analytical methods were used to investigate the similarities and differences of the effects of physical aging on creep compliance of IM7/K3B composite loaded in tension and compression. Two matrix dominated loading modes, shear and transverse, were investigated for two load cases, tension and compression. The tests, run over a range of sub-glass transition temperatures, provided material constants, material master curves and aging related parameters. Comparing results from the short-term data indicated that although trends in the data with respect to aging time and aging temperature are similar, differences exist due to load direction and mode. The analytical model used for predicting long-term behavior using short-term data as input worked equally as well for the tension or compression loaded cases. Comparison of the loading modes indicated that the predictive model provided more accurate long term predictions for the shear mode as compared to the transverse mode. Parametric studies showed the usefulness of the predictive model as a tool for investigating long-term performance and compliance acceleration due to temperature.

Polyaniline-Cadmium Ferrite Nanostructured Composite for Room-Temperature Liquefied Petroleum Gas Sensing

NASA Astrophysics Data System (ADS)

Kotresh, S.; Ravikiran, Y. T.; Tiwari, S. K.; Vijaya Kumari, S. C.

2017-08-01

We introduce polyaniline-cadmium ferrite (PANI-CdFe2O4) nanostructured composite as a room-temperature-operable liquefied petroleum gas (LPG) sensor. The structure of PANI and the composite prepared by chemical polymerization was characterized by Fourier-transform infrared (FT-IR) spectroscopy, x-ray diffraction (XRD) analysis, and field-emission scanning electron microscopy. Comparative XRD and FT-IR analysis confirmed CdFe2O4 embedded in PANI matrix with mutual interfacial interaction. The nanostructure of the composite was confirmed by transmission electron microscopy. A simple LPG sensor operable at room temperature, exclusively based on spin-coated PANI-CdFe2O4 nanocomposite, was fabricated with maximum sensing response of 50.83% at 1000 ppm LPG. The response and recovery time of the sensor were 50 s and 110 s, respectively, and it was stable over a period of 1 month with slight degradation of 4%. The sensing mechanism is discussed on the basis of the p- n heterojunction barrier formed at the interface of PANI and CdFe2O4.

Electrical conductivity of multi-walled carbon nanotubes-SU8 epoxy composites

NASA Astrophysics Data System (ADS)

Grimaldi, Claudio; Mionić, Marijana; Gaal, Richard; Forró, László; Magrez, Arnaud

2013-06-01

We have characterized the electrical conductivity of the composite which consists of multi-walled carbon nanotubes dispersed in SU8 epoxy resin. Depending on the processing conditions of the epoxy (ranging from non-polymerized to cross-linked), we obtained tunneling and percolating-like regimes of the electrical conductivity of the composites. We interpret the observed qualitative change of the conductivity behavior in terms of reduced separation between the nanotubes induced by polymerization of the epoxy matrix.

Nanoconfinement: an effective way to enhance PVDF piezoelectric properties.

PubMed

Cauda, Valentina; Stassi, Stefano; Bejtka, Katarzyna; Canavese, Giancarlo

2013-07-10

The dimensional confinement and oriented crystallization are both key factors in determining the piezoelectric properties of a polymeric nanostructured material. Here we prepare arrays of one-dimensional polymeric nanowires showing piezoelectric features by template-wetting two distinct polymers into anodic porous alumina (APA) membranes. In particular, poly(vinylidene fluoride), PVDF, and its copolymer poly(vinylidene fluoride-trifluoroethylene), PVTF, are obtained in commercially available APA, showing a final diameter of about 200 nm and several micrometers in length, reflecting the templating matrix features. We show that the crystallization of both polymers into a ferroelectric phase is directed by the nanotemplate confinement. Interestingly, the PVDF nanowires mainly crystallize into the β-phase in the nanoporous matrix, whereas the reference thin film of PVDF crystallizes in the α nonpolar phase. In the case of the PVTF nanowires, needle-like crystals oriented perpendicularly to the APA channel walls are observed, giving insight on the molecular orientation of the polymer within the nanowire structure. A remarkable piezoelectric behavior of both 1-D polymeric nanowires is observed, upon recording ferroelectric polarization, hysteresis, and displacement loops. In particular, an outstanding piezoelectric effect is observed for the PVDF nanowires with respect to the polymeric thin film, considering that no poling was carried out. Current versus voltage (I-V) characteristics showed a consistent switching behavior of the ferroelectric polar domains, thus revealing the importance of the confined and oriented crystallization of the polymer in monodimensional nanoarchitectures.

Production and characterization of bacterial cellulose membranes with hyaluronic acid from chicken comb.

PubMed

de Oliveira, Sabrina Alves; da Silva, Bruno Campos; Riegel-Vidotti, Izabel Cristina; Urbano, Alexandre; de Sousa Faria-Tischer, Paula Cristina; Tischer, Cesar Augusto

2017-04-01

The bacterial cellulose (BC), from Gluconacetobacter hansenii, is a biofilm with a high degree of crystallinity that can be used for therapeutic purposes and as a candidate for healing wounds. Hyaluronic acid (HA) is a constitutive polysaccharide found in the extracellular matrix and is a material used in tissue engineering and scaffolding for tissue regeneration. In this study, polymeric composites were produced in presence of hyaluronic acid isolated from chicken comb on different days of fermentation, specifically on the first (BCHA-SABT0) and third day (BCHA-SABT3) of fermentation. The structural characteristics, thermal stability and molar mass of hyaluronic acid from chicken comb were evaluated. Native membrane and polymeric composites were characterized with respect to their morphology and crystallinity. The optimized process of extraction and purification of hyaluronic acid resulted in low molar mass hyaluronic acid with structural characteristics similar to the standard commercial hyaluronic acid. The results demonstrate that the polymeric composites (BC/HA-SAB) can be produced in situ. The membranes produced on the third day presented better incorporation of HA-SAB between cellulose microfiber, resulting in membranes with higher thermal stability, higher roughness and lower crystallinity. The biocompatiblily of bacterial cellulose and the importance of hyaluronic acid as a component of extracellular matrix qualify the polymeric composites as promising biomaterials for tissue engineering. Copyright © 2017 Elsevier B.V. All rights reserved.

Method of Preparing Polymers with Low Melt Viscosity

NASA Technical Reports Server (NTRS)

Jensen, Brian J. (Inventor)

2001-01-01

This invention is an improvement in standard polymerizations procedures, i.e., addition-type and step-growth type polymerizations, wherein monomers are reacted to form a growing polymer chain. The improvement includes employing an effective amount of a trifunctional monomer (such as a trifunctional amine anhydride, or phenol) in the polymerization procedure to form a mixture of polymeric materials consisting of branced polymers, star-shaped polymers, and linear polymers. This mixture of polymeric materials has a lower melt temperature and a lower melt viscosity than corresponding linear polymeric materials of equivalent molecular weight.

Insulation Materials Comprising Fibers Having a Partially Cured Polymer Coating Thereon, Articles Including Such Insulation Materials, and Methods of Forming Such Materials and Articles

NASA Technical Reports Server (NTRS)

Morgan, Richard E. (Inventor); Meeks, Craig L. (Inventor)

2017-01-01

Insulation materials have a coating of a partially cured polymer on a plurality of fibers, and the plurality of coated fibers in a cross-linked polymeric matrix. Insulation may be formed by applying a preceramic polymer to a plurality of fibers, heating the preceramic polymer to form a partially cured polymer over at least portions of the plurality of fibers, disposing the plurality of fibers in a polymeric material, and curing the polymeric material. A rocket motor may be formed by disposing a plurality of coated fibers in an insulation precursor, curing the insulation precursor to form an insulation material without sintering the partially cured polymer, and providing an energetic material over the polymeric material. An article includes an insulation material over at least one surface.

Self-Healing of biocompatible polymeric nanocomposities

NASA Astrophysics Data System (ADS)

Espino, Omar; Chipara, Dorina

2014-03-01

Polymers are vulnerable to damage in form of cracks deep within the structure, where detection is difficult and repair is near to impossible. These cracks lead to mechanical degradation of the polymer. A method has been created to solve this problem named polymeric self healing. Self healing capabilities implies the dispersion within the polymeric matrix of microcapsules filled with a monomer and of catalyst. Poly urea-formaldehyde microcapsules used in this method are filled with dicyclopentadiene that is liberated after being ruptured by the crack propagation in the material. Polymerization is assisted by a catalyst FGGC that ignites the self healing process. Nanocomposites, such as titanium oxide, will be used as an integration of these polymers that will be tested by rupturing mechanically slowly. In order to prove the self healing process, Raman spectroscopy, FTIR, and SEM are used.

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy.

PubMed

Marín-Yaseli, Margarita R; Moreno, Miguel; de la Fuente, José L; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-15

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH 4 CN and NaCN, at middle temperatures between 4 and 38°C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH 4 CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study. Copyright © 2017 Elsevier B.V. All rights reserved.

Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy

NASA Astrophysics Data System (ADS)

Marín-Yaseli, Margarita R.; Moreno, Miguel; de la Fuente, José L.; Briones, Carlos; Ruiz-Bermejo, Marta

2018-02-01

HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH4CN and NaCN, at middle temperatures between 4 and 38 °C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH4CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study.

Finite element analysis of heat generation from different light-polymerization sources during cementation of all-ceramic crowns.

PubMed

Tunc, Elif Pak

2007-06-01

Exothermic composite resin chemical reactions and visible light generators can produce heat during a restorative polymerization process. These thermal changes in restored teeth may cause pain and irreversible pulpitis. The purpose of this study was to analyze the temperature distribution and heat flow patterns of a crowned mandibular second premolar tooth model using 3 different light-polymerization technologies and a finite element technique. A 2-dimensional finite element model was used to simulate a clinical condition. Heat flow and thermal stress distribution in a tooth during cementation of an all-ceramic crown using 4 commercially available light-polymerization units (LPUs), each with different wavelengths (Elipar TriLight, Elipar Freelight, Apollo 95 E, and ADT 1000 PAC), were investigated. The temperature values were measured at 3, 10, 12, and 40 seconds for each light-polymerizing unit (LPU) at 6 different finite element nodes. Two-dimensional temporal and spatial distribution of the thermal stress within the tooth, including the thermal coefficients and boundary conditions of the dental materials, were obtained and evaluated. The temperature at the nodal points did not exceed 42 degrees C, which is a threshold value for tissue vitality within the recommended operating periods at the dentin and pulp surface for all LPUs, except for Elipar TriLight. In the case of Elipar TriLlight, the temperatures at the dentin and pulp surfaces were 47 degrees C and 42 degrees C, respectively. When the light-polymerization units were used according to the manufacturers' operating procedures and without prolonged operating periods, with the exception of Elipar TriLight, the investigated LPUs did not produce significant heat. However, when the operating periods were prolonged, unacceptable temperature increases were observed, especially with the high-intensity LPUs.

Radical-Mediated Enzymatic Polymerizations

PubMed Central

Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

2016-01-01

Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

Durability Characterization of Advanced Polymeric Composites at Cryogenic Temperatures

NASA Technical Reports Server (NTRS)

Gates, T. S.

2001-01-01

The next generation of reusable launch vehicles will require technology development in several key areas. Of these key areas, the development of polymeric composite cryogenic fuel tanks promises to present one of the most difficult technical challenges. It is envisioned that a polymer matrix composite (PMC) tank would be a large shell structure capable of containing cryogenic fuels and carrying a range of structural loads. The criteria that will be imposed on such a design include reduced weight, conformal geometry, and impermeability. It is this last criterion, impermeability, that will provide the focus of this paper. The essence of the impermeability criterion is that the tank remains leak free throughout its design lifetime. To address this criterion, one of the first steps is to conduct a complete durability assessment of the PMC materials. At Langley Research Center, a durability assessment of promising new polyimide-based PMCs is underway. This durability program has focused on designing a set of critical laboratory experiments that will determine fundamental material properties under combined thermal-mechanical loading at cryogenic temperatures. The test program provides measurements of lamina and laminate properties, including strength, stiffness, and fracture toughness. The performance of the PMC materials is monitored as a function of exposure conditions and aging time. Residual properties after exposure are measured at cryogenic temperatures and provide quantitative values of residual strength and stiffness. Primary degradation mechanisms and the associated damage modes are measured with both destructive and nondestructive techniques. In addition to mechanical properties, a range of physical properties, such as weight, glass transition, and crack density, are measured and correlated with the test conditions. This paper will report on the progress of this research program and present critical results and illustrative examples of current findings.

Enhancement of thermal and mechanical properties of poly(MMA-co-BA)/Cloisite 30B nanocomposites by ultrasound-assisted in-situ emulsion polymerization.

PubMed

Sharma, Sachin; Kumar Poddar, Maneesh; Moholkar, Vijayanand S

2017-05-01

This study reports synthesis and characterization of poly(MMA-co-BA)/Cloisite 30B (organo-modified montmorillonite clay) nanocomposites by ultrasound-assisted in-situ emulsion polymerization. Copolymers have been synthesized with MMA:BA monomer ratio of 4:1, and varying clay loading (1-5wt% monomer). The poly(MMA-co-BA)/Cloisite 30B nanocomposites have been characterized for their thermal and mechanical properties. Ultrasonically synthesized nanocomposites have been revealed to possess higher thermal degradation resistance and mechanical strength than the nanocomposites synthesized using conventional techniques. These properties, however, show an optimum (or maxima) with clay loading. The maximum values of thermal and mechanical properties of the nanocomposites with optimum clay loading are as follows. Thermal degradation temperatures: T 10% =320°C (4wt%), T 50 =373°C (4wt%), maximum degradation temperature=384°C (4wt%); glass transition temperature=64.8°C (4wt%); tensile strength=20MPa (2wt%), Young's modulus=1.31GPa (2wt%), Percentage elongation=17.5% (1wt%). Enhanced properties of poly(MMA-co-BA)/Cloisite 30B nanocomposites are attributed to effective exfoliation and dispersion of clay nanoparticles in copolymer matrix due to intense micro-convection induced by ultrasound and cavitation. Clay platelets help in effective heat absorption with maximum surface interaction/adhesion that results in increased thermal resistivity of nanocomposites. Hindered motion of the copolymer chains due to clay platelets results in enhancement of tensile strength and Young's modulus of nanocomposite. Rheological (liquid) study of the nanocomposites reveals that nanocomposites have higher yield stress and infinite shear viscosity than neat copolymer. Nonetheless, nanocomposites still display shear thinning behavior - which is typical of the neat copolymer. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis and characterization of microparticles based on poly-methacrylic acid with glucose oxidase for biosensor applications.

PubMed

Hervás Pérez, J P; López-Ruiz, B; López-Cabarcos, E

2016-01-01

In the line of the applicability of biocompatible monomers pH and temperature dependent, we assayed poly-methacrylic acid (p-MAA) microparticles as immobilization system in the design of enzymatic biosensors. Glucose oxidase was used as enzyme model for the study of microparticles as immobilization matrices and as biological material in the performance of glucose biosensors. The enzyme immobilization method was optimized by investigating the influence of monomer concentration and cross-linker content (N',N'-methylenebisacrylamide), used in the preparation of the microparticles in the response of the biosensors. The kinetics of the polymerization and the effects of the temperature were studied, also the conversion of the polymerization was determinates by a weight method. The structure of the obtained p-MAA microparticles were studied through scanning electron microscopy (SEM) and differential scanning microscopy (DSC). The particle size measurements were performed with a Galai-Cis 1 particle analyzer system. Furthermore, the influence of the swelling behavior of hydrogel matrix as a function of pH and temperature were studied. Analytical properties such as sensitivity, linear range, response time and detection limit were studied for the glucose biosensors. The sensitivity for glucose detection obtained with poly-methacrylic acid (p-MAA) microparticles was 11.98mAM(-1)cm(-2) and 10μM of detection limit. A Nafion® layer was used to eliminate common interferents of the human serum such as uric and ascorbic acids. The biosensors were used to determine glucose in human serum samples with satisfactory results. When stored in a frozen phosphate buffer solution (pH 6.0) at -4°C, the useful lifetime of all biosensors was at least 550 days. Copyright © 2015 Elsevier B.V. All rights reserved.

Reduced Crystallization Temperature Methodology for Polymer Selection in Amorphous Solid Dispersions: Stability Perspective.

PubMed

Bhugra, Chandan; Telang, Chitra; Schwabe, Robert; Zhong, Li

2016-09-06

API-polymer interactions, used to select the right polymeric matrix with an aim to stabilize an amorphous dispersion, are routinely studied using spectroscopic and/or calorimetric techniques (i.e., melting point depression). An alternate selection tool has been explored to rank order polymers for formation of stable amorphous dispersions as a pragmatic method for polymer selection. Reduced crystallization temperature of API, a parameter introduced by Zhou et al.,1 was utilized in this study for rank ordering interactions in API-polymeric systems. The trends in reduced crystallization temperature monitored over polymer concentration range of up to 20% polymer loading were utilized to calculate "crystallization parameter" or CP for two model systems (nifedipine and BI ABC). The rank order of CP, i.e., a measure of API-polymer interaction, for nifedipine followed the order PVP > PVP-VA > Soluplus > HPMCAS > PV Ac > PAA. This rank ordering was correlated to published results of molecular interactions and physical stability for nifedipine. A different rank ordering was observed for BI ABC: PAA > PVP > HPMCAS > Soluplus > PVPV-VA > PVAc. Interactions for BI ABC were not as differentiated when compared to nifedipine based on CP trends. BI ABC dispersions at drug loadings between 40 and 60% were physically stable for prolonged periods under ICH conditions as well as accelerated stress. We propose that large CP differences among polymers could be predictive of stability outcomes. Acceptable stability at pharmaceutically relevant drug loadings would suggest that the relative influence of downstream processes, such as polymer solubility in various solvents, process suitability and selection, and more importantly supersaturation potential, should be higher compared to stability considerations while developing compounds like BI ABC.

Myocardial matrix-polyethylene glycol hybrid hydrogels for tissue engineering

NASA Astrophysics Data System (ADS)

Grover, Gregory N.; Rao, Nikhil; Christman, Karen L.

2014-01-01

Similar to other protein-based hydrogels, extracellular matrix (ECM) based hydrogels, derived from decellularized tissues, have a narrow range of mechanical properties and are rapidly degraded. These hydrogels contain natural cellular adhesion sites, form nanofibrous networks similar to native ECM, and are biodegradable. In this study, we expand the properties of these types of materials by incorporating poly(ethylene glycol) (PEG) into the ECM network. We use decellularized myocardial matrix as an example of a tissue specific ECM derived hydrogel. Myocardial matrix-PEG hybrids were synthesized by two different methods, cross-linking the proteins with an amine-reactive PEG-star and photo-induced radical polymerization of two different multi-armed PEG-acrylates. We show that both methods allow for conjugation of PEG to the myocardial matrix by gel electrophoresis and infrared spectroscopy. Scanning electron microscopy demonstrated that the hybrid materials still contain a nanofibrous network similar to unmodified myocardial matrix and that the fiber diameter is changed by the method of PEG incorporation and PEG molecular weight. PEG conjugation also decreased the rate of enzymatic degradation in vitro, and increased material stiffness. Hybrids synthesized with amine-reactive PEG had gelation rates of 30 min, similar to the unmodified myocardial matrix, and incorporation of PEG did not prevent cell adhesion and migration through the hydrogels, thus offering the possibility to have an injectable ECM hydrogel that degrades more slowly in vivo. The photo-polymerized radical systems gelled in 4 min upon irradiation, allowing 3D encapsulation and culture of cells, unlike the soft unmodified myocardial matrix. This work demonstrates that PEG incorporation into ECM-based hydrogels can expand material properties, thereby opening up new possibilities for in vitro and in vivo applications.

Low-melting elemental metal or fusible alloy encapsulated polymerization initiator for delayed initiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hermes, Robert E.

2017-08-15

An encapsulated composition for polymerization includes an initiator composition for initiating a polymerization reaction, and a capsule prepared from an elemental metal or fusible alloy having a melting temperature from about 20.degree. C. to about 200.degree. C. A fluid for polymerization includes the encapsulated composition and a monomer. When the capsule melts or breaks open, the initiator is released.

Probing matrix and tumor mechanics with in situ calibrated optical trap based active microrheology

NASA Astrophysics Data System (ADS)

Staunton, Jack Rory; Vieira, Wilfred; Tanner, Kandice; Tissue Morphodynamics Unit Team

Aberrant extracellular matrix deposition and vascularization, concomitant with proliferation and phenotypic changes undergone by cancer cells, alter mechanical properties in the tumor microenvironment during cancer progression. Tumor mechanics conversely influence progression, and the identification of physical biomarkers promise improved diagnostic and prognostic power. Optical trap based active microrheology enables measurement of forces up to 0.5 mm within a sample, allowing interrogation of in vitro biomaterials, ex vivo tissue sections, and small organisms in vivo. We fabricated collagen I hydrogels exhibiting distinct structural properties by tuning polymerization temperature Tp, and measured their shear storage and loss moduli at frequencies 1-15k Hz at multiple amplitudes. Lower Tp gels, with larger pore size but thicker, longer fibers, were stiffer than higher Tp gels; decreasing strain increased loss moduli and decreased storage moduli at low frequencies. We subcutanously injected probes with metastatic murine melanoma cells into mice. The excised tumors displayed storage and loss moduli 40 Pa and 10 Pa at 1 Hz, increasing to 500 Pa and 1 kPa at 15 kHz, respectively.

PES-Kaolin Mixed Matrix Membranes for Arsenic Removal from Water

PubMed Central

Russo, Francesca; Rezzouk, Lina

2017-01-01

The aim of this work was the fabrication and the characterization of mixed matrix membranes (MMMs) for arsenic (As) removal from water. Membrane separation was combined with an adsorption process by incorporating the kaolin (KT2) Algerian natural clay in polymeric membranes. The effects of casting solution composition was explored using different amounts of polyethersufone (PES) as a polymer, polyvinyl-pyrrolidone (PVP K17) and polyethylene glycol (PEG 200) as pore former agents, N-methyl pyrrolidone (NMP) as a solvent, and kaolin. Membranes were prepared by coupling Non-solvent Induced Phase Separation and Vapour Induced Phase Separation (NIPS and VIPS, respectively). The influence of the exposure time to controlled humid air and temperature was also investigated. The MMMs obtained were characterized in terms of morphology, pore size, porosity, thickness, contact angle and pure water permeability. Adsorption membrane-based tests were carried out in order to assess the applicability of the membranes produced for As removal from contaminated water. Among the investigated kaolin concentrations (ranging from 0 wt % to 5 wt %), a content of 1.25 wt % led to the MMM with the most promising performance. PMID:28974009

Structural modifications of polymethacrylates: impact on thermal behavior and release characteristics of glassy solid solutions.

PubMed

Claeys, Bart; De Coen, Ruben; De Geest, Bruno G; de la Rosa, Victor R; Hoogenboom, Richard; Carleer, Robert; Adriaensens, Peter; Remon, Jean Paul; Vervaet, Chris

2013-11-01

Polymethacrylates such as Eudragit® polymers are well established as drug delivery matrix. Here, we synthesize several Eudragit E PO (n-butyl-, dimethylaminoethyl-, methyl-methacrylate-terpolymer) analogues via free radical polymerization. These polymers are processed via hot melt extrusion, followed by injection molding and evaluated as carriers to produce immediate release solid solution tablets. Three chemical modifications increased the glass transition temperature of the polymer: (a) substitution of n-butyl by t-butyl groups, (b) reduction of the dimethylaminoethyl methacrylate (DMAEMA) content, and (c) incorporation of a bulky isobornyl repeating unit. These structural modifications revealed the possibility to increase the mechanical stability of the tablets via altering the polymer Tg without influencing the drug release characteristics and glassy solid solution forming properties. The presence of DMAEMA units proved to be crucial with respect to API/polymer interaction (essential in creating glassy solid solutions) and drug release characteristics. Moreover, these chemical modifications accentuate the need for a more rational design of (methacrylate) polymer matrix excipients for drug formulation via hot melt extrusion and injection molding. Copyright © 2013 Elsevier B.V. All rights reserved.

Magnetic nanocomposites based on phosphorus-containing polymers—structural characterization and thermal analysis

NASA Astrophysics Data System (ADS)

Alosmanov, R. M.; Szuwarzyński, M.; Schnelle-Kreis, J.; Matuschek, G.; Magerramov, A. M.; Azizov, A. A.; Zimmermann, R.; Zapotoczny, S.

2018-04-01

Fabrication of magnetic nanocomposites containing iron oxide nanoparticles formed in situ within a phosphorus-containing polymer matrix as well as its structural characterization and its thermal degradation is reported here. Comparative structural studies of the parent polymer and nanocomposites were performed using FTIR spectroscopy, x-ray diffraction, and atomic force microscopy. The results confirmed the presence of dispersed iron oxide magnetic nanoparticles in the polymer matrix. The formed composite combines the properties of porous polymer carriers and magnetic particles enabling easy separation and reapplication of such polymeric carriers used in, for example, catalysis or environmental remediation. Studies on thermal degradation of the composites revealed that the process proceeds in three stages while a significant influence of the embedded magnetic particles on that process was observed in the first two stages. Magnetic force microscopy studies revealed that nanocomposites and its calcinated form have strong magnetic properties. The obtained results provide a comprehensive characterization of magnetic nanocomposites and the products of their calcination that are important for their possible applications as sorbents (regeneration conditions, processing temperature, disposal, etc).

Drug-releasing shape-memory polymers - the role of morphology, processing effects, and matrix degradation.

PubMed

Wischke, Christian; Behl, Marc; Lendlein, Andreas

2013-09-01

Shape-memory polymers (SMPs) have gained interest for temporary drug-release systems that should be anchored in the body by self-sufficient active movements of the polymeric matrix. Based on the so far published scientific literature, this review highlights three aspects that require particular attention when combining SMPs with drug molecules: i) the defined polymer morphology as required for the shape-memory function, ii) the strong effects that processing conditions such as drug-loading methodologies can have on the drug-release pattern from SMPs, and iii) the independent control of drug release and degradation by their timely separation. The combination of SMPs with a drug-release functionality leads to multifunctional carriers that are an interesting technology for pharmaceutical sciences and can be further expanded by new materials such as thermoplastic SMPs or temperature-memory polymers. Experimental studies should include relevant molecules as (model) drugs and provide a thermomechanical characterization also in an aqueous environment, report on the potential effect of drug type and loading levels on the shape-memory functionality, and explore the potential correlation of polymer degradation and drug release.

MT1-MMP regulates the turnover and endocytosis of extracellular matrix fibronectin

PubMed Central

Shi, Feng; Sottile, Jane

2011-01-01

The extracellular matrix (ECM) is dynamically remodeled by cells during development, normal tissue homeostasis and in a variety of disease processes. We previously showed that fibronectin is an important regulator of ECM remodeling. The deposition and/or polymerization of fibronectin into the ECM controls the deposition and stability of other ECM molecules. In addition, agents that inhibit fibronectin polymerization promote the turnover of fibronectin fibrils and enhance ECM fibronectin endocytosis and intracellular degradation. Endocytosis of ECM fibronectin is regulated by β1 integrins, including α5β1 integrin. We have examined the role of extracellular proteases in regulating ECM fibronectin turnover. Our data show that membrane type matrix metalloproteinase 1 (MT1-MMP; also known as MMP14) is a crucial regulator of fibronectin turnover. Cells lacking MT1-MMP show reduced turnover and endocytosis of ECM fibronectin. MT1-MMP regulates ECM fibronectin remodeling by promoting extracellular cleavage of fibronectin and by regulating α5β1-integrin endocytosis. Our data also show that fibronectin polymerization stabilizes fibronectin fibrils and inhibits ECM fibronectin endocytosis by inhibiting α5β1-integrin endocytosis. These data are the first to show that an ECM protein and its modifying enzyme can regulate integrin endocytosis. These data also show that integrin trafficking plays a major role in modulating ECM fibronectin remodeling. The dual dependence of ECM fibronectin turnover on extracellular proteolysis and endocytosis highlights the complex regulatory mechanisms that control ECM remodeling to ensure maintenance of proper tissue function. PMID:22159414

Evidence for the in vivo polymerization of ependymin: a brain extracellular glycoprotein.

PubMed

Shashoua, V E; Hesse, G W; Milinazzo, B

1990-07-09

Ependymin, a glycoprotein of the brain extracellular fluid, has been implicated in synaptic changes associated with the consolidation process of long-term memory formation and the activity-dependent sharpening of connections of regenerating optic nerve. In vitro experiments have demonstrated that ependymin has the capacity to form fibrous insoluble polymers (FIP) when the solvent Ca2+ concentration is reduced by the addition of EGTA. Such products, once formed, do not dissolve in 2% sodium dodecyl sulfate (SDS) in 5 M urea. This property was used to develop a method for isolating brain FIP. A reproducible quantity of FIP was found in goldfish and mouse brain. This was highly concentrated in the synaptosomal fraction and had identical immunoreactivity properties to FIP obtained by the polymerization of pure ependymin in vitro as well as a cross-reactivity to other protein components of the extracellular matrix such as fibronectin and laminin. Labeling studies with [35S]methionine showed that labeled FIP aggregates are synthesized in vivo and become associated with the synaptosomal fraction. A comparison of the amino acid sequence of ependymin with those for proteins of the extracellular matrix indicated that common sequences 5-6 amino acids long exist in the molecules. These homologies may explain why antibodies to fibronectin, laminin and tubulin can recognize the FIP prepared from pure ependymin. These results suggest that ependymin can polymerize in vivo to form FIP aggregates which have similar immunoreactivity properties to major components of the brain extracellular matrix.

Encapsulation of Ethylene Gas into Granular Cold-Water-Soluble Starch: Structure and Release Kinetics.

PubMed

Shi, Linfan; Fu, Xiong; Tan, Chin Ping; Huang, Qiang; Zhang, Bin

2017-03-15

Ethylene gas was introduced into granular cold-water-soluble (GCWS) starches using a solid encapsulation method. The morphological and structural properties of the novel inclusion complexes (ICs) were characterized using scanning electron microscopy, X-ray diffractometry, and Raman spectroscopy. The V-type single helix of GCWS starches was formed through controlled gelatinization and ethanol precipitation and was approved to host ethylene gas. The controlled release characteristics of ICs were also investigated at various temperature and relative humidity conditions. Avrami's equation was fitted to understand the release kinetics and showed that the release of ethylene from the ICs was accelerated by increasing temperature or RH and was decelerated by increased degree of amylose polymerization. The IC of Hylon-7 had the highest ethylene concentration (31.8%, w/w) among the five starches, and the IC of normal potato starch showed the best controlled release characteristics. As a renewable and inexpensive material, GCWS starch is a desirable solid encapsulation matrix with potential in agricultural and food applications.

Surface and interface investigation of aluminosilicate biomaterial by the “in vivo” experiments

NASA Astrophysics Data System (ADS)

Oudadesse, H.; Derrien, A. C.; Martin, S.; Chaair, H.; Cathelineau, G.

2008-11-01

Porous mixtures of aluminosilicate/calcium phosphate have been studied for biomaterials applications. Aluminosilicates formed with an inorganic polymeric constitution present amorphous zeolites because of their 3D network structure and present the ability to link to bone matrix. Amorphous geopolymers of the potassium-poly(sialate)-nanopolymer type were synthesised at low temperature and studied for their use as potential biomaterials. They were mixed with 13% weight of calcium phosphate like biphasic hydroxyapatite and β-tricalcium phosphate. In this study, " in vivo" experiments were monitored to evaluate the biocompatibility, the surface and the interface behaviour of these composites when used as bone implants. Moreover, it has been demonstrated using histological and physicochemical studies that the developed materials exhibited a remarkable bone bonding when implanted in a rabbit's thighbone for a period of 1 month. The easy synthesis conditions (low temperature) of this composite and the fast intimate links with bone constitute an improvement of synthetic bone graft biomaterial.

Innovative cellular distance structures from polymeric and metallic threads

NASA Astrophysics Data System (ADS)

Wieczorek, F.; Trümper, W.; Cherif, C.

2017-10-01

Knitting allows a high individual adaptability of the geometry and properties of flat-knitted spacer fabrics. This offers advantages for the specific adjustment of the mechanical properties of innovative composites based on highly viscous matrix systems such as bone cement, elastomer or foam and cellular reinforcing structures made from e. g. polymeric monofilaments or metallic wires. The prerequisite is the availability of binding solutions for highly productive production of functional, cellular, self-stabilized spacer flat knitted fabrics as supporting and functionalized structures.

Dispersion of Single Wall Carbon Nanotubes by in situ Polymerization Under Sonication

NASA Technical Reports Server (NTRS)

Park, Cheol; Ounaies, Zoubeida; Watson, Kent A.; Crooks, Roy E.; Smith, Joseph, Jr.; Lowther, Sharon E.; Connell, John W.; Siochi, Emilie J.; Harrison, Joycelyn S.; St.Clair, Terry L.

2002-01-01

Single wall nanotube reinforced polyimide nanocomposites were synthesized by in situ polymerization of monomers of interest in the presence of sonication. This process enabled uniform dispersion of single wall carbon nanotube (SWNT) bundles in the polymer matrix. The resultant SWNT-polyimide nanocomposite films were electrically conductive (antistatic) and optically transparent with significant conductivity enhancement (10 orders of magnitude) at a very low loading (0.1 vol%). Mechanical properties as well as thermal stability were also improved with the incorporation of the SWNT.

Accelerated cell-sheet recovery from a surface successively grafted with polyacrylamide and poly(N-isopropylacrylamide).

PubMed

Akiyama, Yoshikatsu; Kikuchi, Akihiko; Yamato, Masayuki; Okano, Teruo

2014-08-01

A double polymeric nanolayer consisting of poly(N-isopropylacrylamide) (PIPAAm) and hydrophilic polyacrylamide (PAAm) was deposited on tissue culture polystyrene (TCPS) surfaces using electron beam irradiation to form a new temperature-responsive cell culture surface in which the basal hydrophilic PAAm component in the double polymeric layer promotes the hydration of the upper PIPAAm layer and induces rapid cell detachment compared to a conventional temperature-responsive cell culture surface, PIPAAm-grafted TCPS (PIPAAm-TCPS). Take-off angle-dependent X-ray photoelectron spectroscopy spectral analysis demonstrated that the grafted PIPAAm and PAAm components were located in the upper and basal regions of the double polymeric layer, respectively, suggesting that the double polymeric layer forms an inter-penetrating-network-like structure with PAAm at the basal portion of the PIPAAm grafted chains. The wettability of the temperature-responsive cell culture surfaces with the double polymeric layer tended to be more hydrophilic, with an increase in the basal PAAm graft density at a constant PIPAAm graft density. However, when the graft densities of the upper PIPAAm and basal PAAm were optimized, the resulting temperature-responsive cell culture surface with the double polymeric layer exhibited rapid cell detachment while maintaining cell adhesive character comparable to that of PIPAAm-TCPS. The cell adhesive character was altered from cell-adhesive to cell-repellent with increasing PAAm or PIPAAm graft density. The cell adhesive character of the temperature-responsive cell culture surfaces was relatively consistent with their contact angles. These results strongly suggest that the basal PAAm surface properties affect the degree of hydration and dehydration of the subsequently grafted PIPAAm. In addition, the roles of the hydrophilic component in accelerating cell detachment are further discussed in terms of the mobility of the grafted PIPAAm chains. Applications of this insight might be useful for designing temperature-responsive cell culture surfaces for achieving efficient cell culture and quick target cell detachment. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Advances in joining newer structural materials; Proceedings of the International Conference, Montreal, Canada, July 23-25, 1990

NASA Astrophysics Data System (ADS)

The present conference on advances in joining novel structural materials encompasses such material types as ceramics, plastics and composites, and new metallic materials. Specific issues addressed include the use of conductor electric explosion to join ceramics, the effects of brazing temperature on joint properties of SiC-fiber-reinforced Al-alloy-matrix composites, the in situ structure control of composite materials, and the weldability of polymeric materials that are heterogeneous as to chemical nature from the standpoint of morphology. Also addressed are the joining of the Al-Li alloy 8090, diffusion bonding of a creep-resistant Fe-ODS alloy, the adhesive bonding of zinc-coated steel sheets, welds in thermoplastic composite materials, and hot-melt joints for carbon-fiber-reinforced composites.

Effects of LDEF flight exposure on selected polymer matrix resin composite materials

NASA Technical Reports Server (NTRS)

Slemp, Wayne S.; Young, Philip R.; Witte, William G., Jr.; Shen, James Y.

1991-01-01

The characterization of selected graphite fiber reinforced epoxy and polysulfone matrix resin composites which received exposure to the LEO environment on the LDEF is reported. The changes in mechanical properties of ultimate tensile strength and tensile modulus for exposed flight specimens are compared to the three sets of control specimens. Marked changes in surface appearance are discussed, and resin loss is reported. The chemical characterization including IR, thermal, and selected solution property measurements showed that the molecular structure of the polymeric matrix had not changed significantly in response to this exposure.

Indirect fabrication of multiple post-and-core patterns with a vinyl polysiloxane matrix.

PubMed

Sabbak, Sahar Asaad

2002-11-01

In the described technique, a vinyl polysiloxane material is used as a matrix for the indirect fabrication of multiple custom-cast posts and cores. The matrix technique enables the clinician to fabricate multiple posts and cores in a short period of time. The form, harmony, and common axis of preparation for all cores are well controlled before the definitive crown/fixed partial denture restorations are fabricated. Oral tissues are not exposed to the heat of polymerization or the excess monomer of the resin material when this technique is used.

A dual pH and temperature responsive polymeric fluorescent sensor and its imaging application in living cells.

PubMed

Yin, Liyan; He, Chunsheng; Huang, Chusen; Zhu, Weiping; Wang, Xin; Xu, Yufang; Qian, Xuhong

2012-05-11

A polymeric fluorescent sensor PNME, consisting of A4 and N-isopropylacrylamide (NIPAM) units, was synthesized. PNME exhibited dual responses to pH and temperature, and could be used as an intracellular pH sensor for lysosomes imaging. Moreover, it also could sense different temperature change in living cells at 25 and 37 °C, respectively. This journal is © The Royal Society of Chemistry 2012

Boron/Carbon/Silicon/Nitrogen Ceramics And Precursors

NASA Technical Reports Server (NTRS)

Riccitiello, Salvatore; Hsu, Ming TA; Chen, Timothy S.

1996-01-01

Ceramics containing various amounts of boron, carbon, silicon, and nitrogen made from variety of polymeric precursors. Synthesized in high yield from readily available and relatively inexpensive starting materials. Stable at room temperature; when polymerized, converted to ceramics in high yield. Ceramics resist oxidation and other forms of degradation at high temperatures; used in bulk to form objects or to infiltrate other ceramics to obtain composites having greater resistance to oxidation and high temperatures.

On the Use of Accelerated Aging Methods for Screening High Temperature Polymeric Composite Materials

NASA Technical Reports Server (NTRS)

Gates, Thomas S.; Grayson, Michael A.

1999-01-01

A rational approach to the problem of accelerated testing of high temperature polymeric composites is discussed. The methods provided are considered tools useful in the screening of new materials systems for long-term application to extreme environments that include elevated temperature, moisture, oxygen, and mechanical load. The need for reproducible mechanisms, indicator properties, and real-time data are outlined as well as the methodologies for specific aging mechanisms.

Micropatterning hydroxy-PAAm hydrogels and Sylgard 184 silicone elastomers with tunable elastic moduli.

PubMed

Versaevel, Marie; Grevesse, Thomas; Riaz, Maryam; Lantoine, Joséphine; Gabriele, Sylvain

2014-01-01

This protocol describes a simple method to deposit protein micropatterns over a wide range of culture substrate stiffness (three orders of magnitude) by using two complementary polymeric substrates. In the first part, we introduce a novel polyacrylamide hydrogel, called hydroxy-polyacrylamide (PAAm), that permits to surmount the intrinsically nonadhesive properties of polyacrylamide with minimal requirements in cost or expertize. We present a protocol for tuning easily the rigidity of "soft" hydroxy-PAAm hydrogels between ~0.5 and 50 kPa and a micropatterning method to locally deposit protein micropatterns on these hydrogels. In a second part, we describe a protocol for tuning the rigidity of "stiff" silicone elastomers between ~100 and 1000 kPa and printing efficiently proteins from the extracellular matrix. Finally, we investigate the effect of the matrix rigidity on the nucleus of primary endothelial cells by tuning the rigidity of both polymeric substrates. We envision that the complementarity of these two polymeric substrates, combined with an efficient microprinting technique, can be further developed in the future as a powerful mechanobiology platform to investigate in vitro the effect of mechanotransduction cues on cellular functions, gene expression, and stem cell differentiation. Copyright © 2014 Elsevier Inc. All rights reserved.

Sorption of small molecules in polymeric media

NASA Astrophysics Data System (ADS)

Camboni, Federico; Sokolov, Igor M.

2016-12-01

We discuss the sorption of penetrant molecules from the gas phase by a polymeric medium within a model which is very close in spirit to the dual sorption mode model: the penetrant molecules are partly dissolved within the polymeric matrix, partly fill the preexisting voids. The only difference with the initial dual sorption mode situation is the assumption that the two populations of molecules are in equilibrium with each other. Applying basic thermodynamics principles we obtain the dependence of the penetrant concentration on the pressure in the gas phase and find that this is expressed via the Lambert W-function, a different functional form than the one proposed by dual sorption mode model. The Lambert-like isotherms appear universally at low and moderate pressures and originate from the assumption that the internal energy in a polymer-penetrant-void ternary mixture is (in the lowest order) a bilinear form in the concentrations of the three components. Fitting the existing data shows that in the domain of parameters where the dual sorption mode model is typically applied, the Lambert function, which describes the same behavior as the one proposed by the gas-polymer matrix model, fits the data equally well.

Effect of polyvinyl siloxane impression material on the polymerization of composite resin.

PubMed

Chen, Liang; Kleverlaan, Cornelis Johannes; Liang, Kunneng; Yang, Deqin

2017-04-01

Polyvinyl siloxane impression material has been widely used as a lingual matrix for rebuilding missing tooth structure with composite resin. The composite resin is light polymerized in contact with the polyvinyl siloxane impression material. However, polyvinyl siloxane impression material has been shown to interact with other dental materials. The purpose of this study was to assess the effect of polyvinyl siloxane impression materials on the polymerization of composite resins by assessing the Vickers microhardness and degree of conversion of polyvinyl siloxane. The composite resins were light polymerized in contact with 3 polyvinyl siloxane impression materials (Flexitime Easy Putty; President Light Body; Xantopren L Blue) (n=8) and in contact with a matrix strip as the control group (n=8). Vickers microhardness and degree of conversion on contact surfaces were measured to evaluate the polymerization of composite resins. The depth of the effect was assessed by Vickers microhardness on section surfaces and observed with scanning electron microscopy. The results were analyzed by 1-way analysis of variance and the post hoc Tukey honest significant differences test (α=.05). The Vickers microhardness and degree of conversion values on the contact surfaces of the experiment groups were significantly lower than those of the control group (P<.05); the Vickers microhardness values on the section surfaces indicated that there was no significant difference at the same depth of different groups (P>.05). The scanning electron microscope observation showed that an approximately 10-μm deep unpolymerized layer was found in the experimental group. Polyvinyl siloxane impression materials have an inhibitory effect on the polymerization of the composite resins, but just limited to within approximately 10 μm from the surface in contact with the impression material. Copyright © 2016 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Interference lithography for optical devices and coatings

NASA Astrophysics Data System (ADS)

Juhl, Abigail Therese

Interference lithography can create large-area, defect-free nanostructures with unique optical properties. In this thesis, interference lithography will be utilized to create photonic crystals for functional devices or coatings. For instance, typical lithographic processing techniques were used to create 1, 2 and 3 dimensional photonic crystals in SU8 photoresist. These structures were in-filled with birefringent liquid crystal to make active devices, and the orientation of the liquid crystal directors within the SU8 matrix was studied. Most of this thesis will be focused on utilizing polymerization induced phase separation as a single-step method for fabrication by interference lithography. For example, layered polymer/nanoparticle composites have been created through the one-step two-beam interference lithographic exposure of a dispersion of 25 and 50 nm silica particles within a photopolymerizable mixture at a wavelength of 532 nm. In the areas of constructive interference, the monomer begins to polymerize via a free-radical process and concurrently the nanoparticles move into the regions of destructive interference. The holographic exposure of the particles within the monomer resin offers a single-step method to anisotropically structure the nanoconstituents within a composite. A one-step holographic exposure was also used to fabricate self-healing coatings that use water from the environment to catalyze polymerization. Polymerization induced phase separation was used to sequester an isocyanate monomer within an acrylate matrix. Due to the periodic modulation of the index of refraction between the monomer and polymer, the coating can reflect a desired wavelength, allowing for tunable coloration. When the coating is scratched, polymerization of the liquid isocyanate is catalyzed by moisture in air; if the indices of the two polymers are matched, the coatings turn transparent after healing. Interference lithography offers a method of creating multifunctional self-healing coatings that readout when damage has occurred.

Highly efficient reversible addition-fragmentation chain-transfer polymerization in ethanol/water via flow chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Piaoran; Cao, Peng -Fei; Su, Zhe

Here, utilization of a flow reactor under high pressure allows highly efficient polymer synthesis via reversible addition–fragmentation chain-transfer (RAFT) polymerization in an aqueous system. Compared with the batch reaction, the flow reactor allows the RAFT polymerization to be performed in a high-efficiency manner at the same temperature. The adjustable pressure of the system allows further elevation of the reaction temperature and hence faster polymerization. Other reaction parameters, such as flow rate and initiator concentration, were also well studied to tune the monomer conversion and the molar mass dispersity (Ð) of the obtained polymers. Gel permeation chromatography, nuclear magnetic resonance (NMR),more » and Fourier transform infrared spectroscopies (FTIR) were utilized to monitor the polymerization process. With the initiator concentration of 0.15 mmol L –1, polymerization of poly(ethylene glycol) methyl ethermethacrylate with monomer conversion of 52% at 100 °C under 73 bar can be achieved within 40 min with narrow molar mass dispersity (D) Ð (<1.25). The strategy developed here provides a method to produce well-defined polymers via RAFT polymerization with high efficiency in a continuous manner.« less

Fixation of tritium in a highly stable polymer form

DOEpatents

Steinberg, Meyer; Colombo, Peter; Pruzansky, Jacob

1977-01-01

A method for the fixation of tritium comprising reacting tritiated water with calcium carbide to produce calcium hydroxide and tritiated acetylene, polymerizing the acetylene, and then incorporating the polymer in a solidifying matrix.

Hybrid nanocomposites of 2D black phosphorus nanosheets encapsulated in PMMA polymer material: new platforms for advanced device fabrication

NASA Astrophysics Data System (ADS)

Telesio, Francesca; Passaglia, Elisa; Cicogna, Francesca; Costantino, Federica; Serrano-Ruiz, Manuel; Peruzzini, Maurizio; Heun, Stefan

2018-07-01

Hybrid materials, containing a 2D filler embedded in a polymeric matrix, are an interesting platform for several applications, because of the variety of properties that the filler can impart to the polymer matrix when dispersed at the nanoscale. Moreover, novel properties could arise from the interaction between the two. Mostly the bulk properties of these materials have been studied so far, especially focusing on how the filler changes the polymeric matrix properties. Here we propose a complete change of perspective by using the hybrid nanocomposite material as a platform suitable to engineer the properties of the filler and to exploit its potential in the fabrication of devices. As a proof of concept of the versatility and the potential of the new method, we applied this approach to prepare black phosphorus (bP) nanocomposites through its dispersion in poly (methyl methacrylate). bP is a very interesting 2D material, whose application have so far been limited by its high reactivity to oxygen and water. In this respect, we show that electronic-grade bP flakes, already embedded in a protecting matrix since their exfoliation from the bulk material, are endowed with significantly increased stability and can be further processed into devices without degrading their properties.

Hybrid Nanocomposites of 2D Black Phosphorous Nanosheets Encapsulated in PMMA Polymer Material: New Platforms for Advanced Device Fabrication.

PubMed

Telesio, Francesca; Passaglia, Elisa; Cicogna, Francesca; Costantino, Federica; Serrano-Ruiz, Manuel; Peruzzini, Maurizio; Heun, Stefan

2018-04-12

Hybrid materials, containing a 2D filler embedded in a polymeric matrix, are an interesting platform for several applications, because of the variety of properties that the filler can impart to the polymer matrix when dispersed at the nanoscale. Moreover, novel properties could arise from the interaction between the two. Mostly the bulk properties of these materials have been studied so far, especially focusing on how the filler changes the polymeric matrix properties. Here we propose a complete change of perspective by using the hybrid nanocomposite material as a platform suitable to engineer the properties of the filler and to exploit its potential in the fabrication of devices. As a proof of concept of the versatility and potentiality of the new method, we applied this approach to prepare black phosphorus nanocomposites through its dispersion in poly (methyl methacrylate). Black phosphorus is a very interesting 2D material, whose application have so far been limited by its very high reactivity to oxygen and water. In this respect, we show that electronic-grade black phosphorus flakes, already embedded in a protecting matrix since their exfoliation from the bulk material, are endowed with significant increased stability, and can be further processed into devices without degrading their properties. Creative Commons Attribution license.

Artificial biofilms establish the role of matrix interactions in staphylococcal biofilm assembly and disassembly.

PubMed

Stewart, Elizabeth J; Ganesan, Mahesh; Younger, John G; Solomon, Michael J

2015-08-14

We demonstrate that the microstructural and mechanical properties of bacterial biofilms can be created through colloidal self-assembly of cells and polymers, and thereby link the complex material properties of biofilms to well understood colloidal and polymeric behaviors. This finding is applied to soften and disassemble staphylococcal biofilms through pH changes. Bacterial biofilms are viscoelastic, structured communities of cells encapsulated in an extracellular polymeric substance (EPS) comprised of polysaccharides, proteins, and DNA. Although the identity and abundance of EPS macromolecules are known, how these matrix materials interact with themselves and bacterial cells to generate biofilm morphology and mechanics is not understood. Here, we find that the colloidal self-assembly of Staphylococcus epidermidis RP62A cells and polysaccharides into viscoelastic biofilms is driven by thermodynamic phase instability of EPS. pH conditions that induce phase instability of chitosan produce artificial S. epidermidis biofilms whose mechanics match natural S. epidermidis biofilms. Furthermore, pH-induced solubilization of the matrix triggers disassembly in both artificial and natural S. epidermidis biofilms. This pH-induced disassembly occurs in biofilms formed by five additional staphylococcal strains, including three clinical isolates. Our findings suggest that colloidal self-assembly of cells and matrix polymers produces biofilm viscoelasticity and that biofilm control strategies can exploit this mechanism.

Artificial biofilms establish the role of matrix interactions in staphylococcal biofilm assembly and disassembly

PubMed Central

Stewart, Elizabeth J.; Ganesan, Mahesh; Younger, John G.; Solomon, Michael J.

2015-01-01

We demonstrate that the microstructural and mechanical properties of bacterial biofilms can be created through colloidal self-assembly of cells and polymers, and thereby link the complex material properties of biofilms to well understood colloidal and polymeric behaviors. This finding is applied to soften and disassemble staphylococcal biofilms through pH changes. Bacterial biofilms are viscoelastic, structured communities of cells encapsulated in an extracellular polymeric substance (EPS) comprised of polysaccharides, proteins, and DNA. Although the identity and abundance of EPS macromolecules are known, how these matrix materials interact with themselves and bacterial cells to generate biofilm morphology and mechanics is not understood. Here, we find that the colloidal self-assembly of Staphylococcus epidermidis RP62A cells and polysaccharides into viscoelastic biofilms is driven by thermodynamic phase instability of EPS. pH conditions that induce phase instability of chitosan produce artificial S. epidermidis biofilms whose mechanics match natural S. epidermidis biofilms. Furthermore, pH-induced solubilization of the matrix triggers disassembly in both artificial and natural S. epidermidis biofilms. This pH-induced disassembly occurs in biofilms formed by five additional staphylococcal strains, including three clinical isolates. Our findings suggest that colloidal self-assembly of cells and matrix polymers produces biofilm viscoelasticity and that biofilm control strategies can exploit this mechanism. PMID:26272750

Assembly properties of the Bacillus subtilis actin, MreB.

PubMed

Mayer, Joshua A; Amann, Kurt J

2009-02-01

The bacterial actin MreB has been implicated in a variety of cellular roles including cell shape determination, cell wall synthesis, chromosome condensation and segregation, and the establishment and maintenance of cell polarity. Toward elucidating a clearer understanding of how MreB functions inside the bacterial cell, we investigated biochemically the polymerization of MreB from Bacillus subtilis. Light scattering and sedimentation assays revealed pH-, ionic-, cationic-, and temperature-dependent behavior. B. subtilis MreB polymerizes in the presence of millimolar divalent cations in a protein concentration-dependent manner. Polymerization is favored by decreasing pH and inhibited by monovalent salts and low temperatures. Although B. subtilis MreB binds and hydrolyzes both ATP and GTP, it does not require a bound nucleotide for assembly and polymerizes indistinguishably regardless of the nucleotide species bound, with a critical concentration of approximately 900 nM. A number of the presently reported properties of B. subtilis MreB differ significantly from those of T. maritima MreB1 (Bean and Amann [2008]: Biochemistry 47: 826-835), including the nucleotide requirements and temperature and ionic effects on polymerization state. These observations collectively suggest that additional factors interact with MreB to account for its complex dynamic behavior in cells.

The Role of Network Architecture in Collagen Mechanics.

PubMed

Jansen, Karin A; Licup, Albert J; Sharma, Abhinav; Rens, Robbie; MacKintosh, Fred C; Koenderink, Gijsje H

2018-06-05

Collagen forms fibrous networks that reinforce tissues and provide an extracellular matrix for cells. These networks exhibit remarkable strain-stiffening properties that tailor the mechanical functions of tissues and regulate cell behavior. Recent models explain this nonlinear behavior as an intrinsic feature of disordered networks of stiff fibers. Here, we experimentally validate this theoretical framework by measuring the elastic properties of collagen networks over a wide range of self-assembly conditions. We show that the model allows us to quantitatively relate both the linear and nonlinear elastic behavior of collagen networks to their underlying architecture. Specifically, we identify the local coordination number (or connectivity) 〈z〉 as a key architectural parameter that governs the elastic response of collagen. The network elastic response reveals that 〈z〉 decreases from 3.5 to 3 as the polymerization temperature is raised from 26 to 37°C while being weakly dependent on concentration. We furthermore infer a Young's modulus of 1.1 MPa for the collagen fibrils from the linear modulus. Scanning electron microscopy confirms that 〈z〉 is between three and four but is unable to detect the subtle changes in 〈z〉 with polymerization conditions that rheology is sensitive to. Finally, we show that, consistent with the model, the initial stress-stiffening response of collagen networks is controlled by the negative normal stress that builds up under shear. Our work provides a predictive framework to facilitate future studies of the regulatory effect of extracellular matrix molecules on collagen mechanics. Moreover, our findings can aid mechanobiological studies of wound healing, fibrosis, and cancer metastasis, which require collagen matrices with tunable mechanical properties. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Numerical simulation of hot-melt extrusion processes for amorphous solid dispersions using model-based melt viscosity.

PubMed

Bochmann, Esther S; Steffens, Kristina E; Gryczke, Andreas; Wagner, Karl G

2018-03-01

Simulation of HME processes is a valuable tool for increased process understanding and ease of scale-up. However, the experimental determination of all required input parameters is tedious, namely the melt rheology of the amorphous solid dispersion (ASD) in question. Hence, a procedure to simplify the application of hot-melt extrusion (HME) simulation for forming amorphous solid dispersions (ASD) is presented. The commercial 1D simulation software Ludovic ® was used to conduct (i) simulations using a full experimental data set of all input variables including melt rheology and (ii) simulations using model-based melt viscosity data based on the ASDs glass transition and the physical properties of polymeric matrix only. Both types of HME computation were further compared to experimental HME results. Variation in physical properties (e.g. heat capacity, density) and several process characteristics of HME (residence time distribution, energy consumption) among the simulations and experiments were evaluated. The model-based melt viscosity was calculated by using the glass transition temperature (T g ) of the investigated blend and the melt viscosity of the polymeric matrix by means of a T g -viscosity correlation. The results of measured melt viscosity and model-based melt viscosity were similar with only few exceptions, leading to similar HME simulation outcomes. At the end, the experimental effort prior to HME simulation could be minimized and the procedure enables a good starting point for rational development of ASDs by means of HME. As model excipients, Vinylpyrrolidone-vinyl acetate copolymer (COP) in combination with various APIs (carbamazepine, dipyridamole, indomethacin, and ibuprofen) or polyethylene glycol (PEG 1500) as plasticizer were used to form the ASDs. Copyright © 2017 Elsevier B.V. All rights reserved.

Apparatus and method for stabilization or oxidation of polymeric materials

DOEpatents

Paulauskas, Felix L [Knoxville, TN; Sherman, Daniel M [Knoxville, TN

2010-01-19

An apparatus for treating polymeric materials comprises a treatment chamber adapted to maintain a selected atmosphere at a selected temperature; a means for supporting the polymeric material within the chamber; and, a source of ozone-containing gas, which decomposes at the selected temperature yielding at least one reactive oxidative species whereby the polymer is stabilized and cross linked through exposure to the oxidative species in the chamber at the selected temperature. The ozone may be generated by a plasma discharge or by various chemical processes. The apparatus may be configured for either batch-type or continuous-type processing. The apparatus and method are especially useful for preparing polymer fibers, particularly PAN fibers, for later carbonization treatments as well as to make flame-retardant fabrics.

Temperature-dependent charge transport mechanisms in carbon sphere/polyaniline composite

NASA Astrophysics Data System (ADS)

Nieves, Cesar A.; Martinez, Luis M.; Meléndez, Anamaris; Ortiz, Margarita; Ramos, Idalia; Pinto, Nicholas J.; Zimbovskaya, Natalya

2017-12-01

Charge transport in the temperature range 80 K < T < 300 K was studied in a composite of carbon spheres (CS), prepared via hydrothermal carbonization of sucrose, and the conducting polymer polyaniline (PANi). PANi was synthesized via the oxidative polymerization of aniline with ammonium peroxydisulfate (APS) in acidic media. The CS/PANi composite was prepared by coating the spheres with a thin polyaniline (PANi) film doped with hydrochloric acid (HCl) in situ during the polymerization process. Temperature dependent conductivity measurements show that three dimensional variable range hopping of electrons between polymeric chains in PANi-filled gaps between CS is the predominant transport mechanism through CS/PANi composites. The high conductivity of the CS/PANi composite makes the material attractive for the fabrication of devices and sensors.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hermes, Robert E.

An encapsulated composition for polymerization includes an initiator composition for initiating a polymerization reaction, and a capsule prepared from an elemental metal or fusible alloy having a melting temperature from about 20.degree. C. to about 200.degree. C. A fluid for polymerization includes the encapsulated composition and a monomer. When the capsule melts or breaks open, the initiator is released.

Carbon Dioxide Separation Using Thermally Optimized Membranes

NASA Astrophysics Data System (ADS)

Young, J. S.; Jorgensen, B. S.; Espinoza, B. F.; Weimer, M. W.; Jarvinen, G. D.; Greenberg, A.; Khare, V.; Orme, C. J.; Wertsching, A. K.; Peterson, E. S.; Hopkins, S. D.; Acquaviva, J.

2002-05-01

The purpose of this project is to develop polymeric-metallic membranes for carbon dioxide separations that operate under a broad range of industrially relevant conditions not accessible with present membrane units. The last decade has witnessed a dramatic increase in the use of polymer membranes as an effective, economic and flexible tool for many commercial gas separations including air separation, the recovery of hydrogen from nitrogen, carbon monoxide, and methane mixtures, and the removal of carbon dioxide from natural gas. In each of these applications, high fluxes and excellent selectivities have relied on glassy polymer membranes which separate gases based on both size and solubility differences. To date, however, this technology has focused on optimizing materials for near ambient conditions. The development of polymeric materials that achieve the important combination of high selectivity, high permeability, and mechanical stability at temperatures significantly above 25oC and pressures above 10 bar, respectively, has been largely ignored. Consequently, there is a compelling rationale for the exploration of a new realm of polymer membrane separations. Indeed, the development of high temperature polymeric-metallic composite membranes for carbon dioxide separation at temperatures of 100-450 oC and pressures of 10-150 bar would provide a pivotal contribution with both economic and environmental benefits. Progress to date includes the first ever fabrication of a polymeric-metallic membrane that is selective from room temperature to 370oC. This achievement represents the highest demonstrated operating temperature at which a polymeric based membrane has successfully functioned. Additionally, we have generated the first polybenzamidizole silicate molecular composites. Finally, we have developed a technique that has enabled the first-ever simultaneous measurements of gas permeation and membrane compaction at elevated temperatures. This technique provides a unique approach to the optimization of long-term membrane performance under challenging operating conditions.

Plasma-grafting polymerization on carbon fibers and its effect on their composite properties

NASA Astrophysics Data System (ADS)

Zhang, Huanxia; Li, Wei

2015-11-01

Interfacial adhesion between matrix and fibers plays a crucial role in controlling the performance of composites. Carbon fibers have the major constraint of chemical interness and hence have limited adhesion with the matrix. Surface treatment of fibers is the best solution to this problem. In this work, carbon fibers were activated by plasma and grafting polymerization. The grafting ratio of polymerization was obtained by acid-base titration. The chemical and physical changes induced by the treatments on carbon fiber surface was examined using contact angle measurements, X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy-attenuated total reflectance (FTIR-ATR) technique. The interfacial adhesion of CF/EP (carbon fiber/epoxy) composites were analyzed by a single fiber composite (SFC) for filament fragmentation test. Experimental results show that the grafting rate was not only the function of the plasma-treat time but also the concentration of the grafting polymerization. The oxygen-containing groups (such as Csbnd O, Cdbnd O, and Osbnd Cdbnd O) and the interfacial shear strength (IFSS) of the plasma-grafting carbon fiber increased more significantly than the carbon fiber without plasma treatment grafted with MAH. This demonstrates that the surfaces of the carbon fiber samples are more active, hydrophilic, and rough after plasma-grafting treatments using a DBD operating in ambient argon mixture with oxygen. With DBD (dielectric barrier discharges) operating in ambient argon mixture with oxygen, the more active, hydrophilic, and rough surface was obtained by the plasma-grafting treatments.

A fluorescent colorimetric pH sensor and the influences of matrices on sensing performances

PubMed Central

Tian, Yanqing; Fuller, Emily; Klug, Summer; Lee, Fred; Su, Fengyu; Zhang, Liqiang; Chao, Shih-hui; Meldrum, Deirdre R.

2013-01-01

A fluorescent colorimetric pH sensor was developed by a polymerization of a monomeric fluorescein based green emitter (SM1) with a monomeric 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran derived red emitter (SM2) in poly(2-hydroxyethyl methacrylate)-co-polyacrylamide (PHEMA-co-PAM) matrices. Polymerized SM1 (PSM1) in the polymer matrices showed bright emissions at basic conditions and weak emissions at acidic conditions. Polymerized SM2 (PSM2) in the polymer matrices exhibited a vastly different response when compared to PSM1. The emissions of PSM2 are stronger under acidic conditions than those under basic conditions. When SM1 and SM2 were polymerized in the same polymer matrix, a dual emission sensor acting as a ratiometric pH sensor (PSM1,2) was successfully developed. Because the PSM1 and PSM2 exhibited different pH responses and separated emission windows, the changes in the emission colors were clearly observed in their dual color sensor of PSM1,2, which changed emission colors dramatically from green at pH 7 to red at pH 4, which was detected visually and/or by using a color camera under an excitation of 488 nm. In addition to the development of the dual color ratiometric pH sensor, we also studied the effects of different matrix compositions, crosslinkers, and charges on the reporting capabilities of the sensors (sensitivity and pKa). PMID:24078772

New electrochemiluminescent biosensors combining polyluminol and an enzymatic matrix.

PubMed

Sassolas, Audrey; Blum, Loïc J; Leca-Bouvier, Béatrice D

2009-06-01

Performant reagentless electrochemiluminescent (ECL) (bio)sensors have been developed using polymeric luminol as the luminophore. The polyluminol film is obtained by cyclic voltammetry (CV) on a screen-printed electrode either in a commonly used H(2)SO(4) medium or under more original near-neutral buffered conditions. ECL responses obtained after performing polymerization either at acidic pH or at pH 6 have been compared. It appears that polyluminol formed in near-neutral medium gives the best responses for hydrogen peroxide detection. Polymerization at pH 6 by cyclic voltammetry gives a linear range extending from 8 x 10(-8) to 1.3 x 10(-4) M H(2)O(2) concentrations. Based on this performant sensor for hydrogen peroxide detection, an enzymatic biosensor has been developed by associating the polyluminol film with an H(2)O(2)-producing oxidase. Here, choline oxidase (ChOD) has been chosen as a model enzyme. To develop the biosensor, luminol has been polymerized at pH 6 by CV, and then an enzyme-entrapping matrix has been formed on the above modified working electrode. Different biological (chitosan, agarose, and alginate) and chemical (silica gels, photopolymers, or reticulated matrices) gels have been tested. Best performances have been obtained by associating a ChOD-immobilizing photopolymer with the polyluminol film. In this case, choline can be detected with a linear range extending from 8 x 10(-8) to 1.3 x 10(-4) M.

A fluorescent colorimetric pH sensor and the influences of matrices on sensing performances.

PubMed

Tian, Yanqing; Fuller, Emily; Klug, Summer; Lee, Fred; Su, Fengyu; Zhang, Liqiang; Chao, Shih-Hui; Meldrum, Deirdre R

2013-10-01

A fluorescent colorimetric pH sensor was developed by a polymerization of a monomeric fluorescein based green emitter ( SM1 ) with a monomeric 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran derived red emitter ( SM2 ) in poly(2-hydroxyethyl methacrylate)- co -polyacrylamide (PHEMA-co-PAM) matrices. Polymerized SM1 ( PSM1 ) in the polymer matrices showed bright emissions at basic conditions and weak emissions at acidic conditions. Polymerized SM2 ( PSM2 ) in the polymer matrices exhibited a vastly different response when compared to PSM1 . The emissions of PSM2 are stronger under acidic conditions than those under basic conditions. When SM1 and SM2 were polymerized in the same polymer matrix, a dual emission sensor acting as a ratiometric pH sensor ( PSM1,2 ) was successfully developed. Because the PSM1 and PSM2 exhibited different pH responses and separated emission windows, the changes in the emission colors were clearly observed in their dual color sensor of PSM1,2 , which changed emission colors dramatically from green at pH 7 to red at pH 4, which was detected visually and/or by using a color camera under an excitation of 488 nm. In addition to the development of the dual color ratiometric pH sensor, we also studied the effects of different matrix compositions, crosslinkers, and charges on the reporting capabilities of the sensors (sensitivity and p K a ).

Cell for making secondary batteries

DOEpatents

Visco, Steven J.; Liu, Meilin; DeJonghe, Lutgard C.

1992-01-01

The present invention provides all solid-state lithium and sodium batteries operating in the approximate temperature range of ambient to 145.degree. C. (limited by melting points of electrodes/electrolyte), with demonstrated energy and power densities far in excess of state-of-the-art high-temperature battery systems. The preferred battery comprises a solid lithium or sodium electrode, a polymeric electrolyte such as polyethylene oxide doped with lithium triflate (PEO.sub.8 LiCF.sub.3 SO.sub.3), and a solid-state composite positive electrode containing a polymeric organosulfur electrode, (SRS).sub.n, and carbon black, dispersed in a polymeric electrolyte.

Cell for making secondary batteries

DOEpatents

Visco, S.J.; Liu, M.; DeJonghe, L.C.

1992-11-10

The present invention provides all solid-state lithium and sodium batteries operating in the approximate temperature range of ambient to 145 C (limited by melting points of electrodes/electrolyte), with demonstrated energy and power densities far in excess of state-of-the-art high-temperature battery systems. The preferred battery comprises a solid lithium or sodium electrode, a polymeric electrolyte such as polyethylene oxide doped with lithium trifluorate (PEO[sub 8]LiCF[sub 3]SO[sub 3]), and a solid-state composite positive electrode containing a polymeric organosulfur electrode, (SRS)[sub n], and carbon black, dispersed in a polymeric electrolyte. 2 figs.

Low Temperature, Low Pressure Fabrication of Ultra High Temperature Ceramics (UHTCs)

DTIC Science & Technology

2006-08-01

preceramic polymers that convert by pyrolysis to SiC , SiOC or C. Potential polymeric precursors to ZrB2 and ZrC were not selected, because they were not...limited extent, C/ SiC composite substrates using preceramic and precarbon polymers combined with inert fillers and/or reactive metals. The evolved... SiC is an obvious example for powder mixed with a preceramic polymer binder to achieve the desired low-temperature processing. The polymeric

Adhesion and Interphase Properties of Reinforced Polymeric Composites

NASA Astrophysics Data System (ADS)

Caldwell, Kyle Bernd

Reinforced polymeric composites are an increasingly utilized material with a wide range of applications. Fiber reinforced polymeric composites, in particular, possess impressive mechanical properties at a fraction of the weight of many other building materials. There will always, however, be a demand for producing lighter, stiffer, and stronger materials. Understanding the mechanism of adhesion and ways to engineer the reinforcement-matrix interphase can lead to the development of new materials with improved mechanical properties, and even impart additional functionality such as electrical conductivity. The performance of reinforced polymeric composites is critically dependent upon the adhesion between the reinforcement and the surrounding polymer. The relative adhesion between a filler and a thermoplastic matrix can be predicted using calculable thermodynamic quantities such as the Gibbs free energy of mixing. A recent model, COSMO-SAC, is capable of predicting the adhesion between organo-silane treated glass surfaces and several thermoplastic materials. COSMO-SAC uses information based on the charge distribution of a molecule's surface to calculate many thermodynamic properties. Density functional theory calculations, which are relative inexpensive computations, generate the information necessary to perform the COSMO-SAC analysis and can be performed on any given molecule. The flexibility of the COSMO-SAC model is one of the main advantages it possesses over other methods for calculating thermodynamic quantities. In many cases the adhesion between a reinforcing fiber and the surrounding matrix may be improved by incorporating interphase modifiers in the vicinity of the fiber surface. The modifiers can improve the fracture toughness and modulus of the interphase, which may improve the stress transfer from the matrix to the fiber. In addition, the interphase modifiers may improve the mechanical interlock between the fiber surface and the bulk polymer, leading to improved adhesion. In recent years, the use of so called "migrating agents" have been used to self-assemble nanoparticle reinforced fiber-matrix interphases in thermosetting resin systems. The inclusion of a modest amount of thermoplastic migrating agent can lead to the formation of a self-assembled interphase, without causing aggregation of nanoparticles in the bulk phase. Formulations containing excess migrating agent, however, can induce aggregation in the bulk of increasing severity with increasing migrating agent concentration. Several techniques were used to study the mechanism by which the migrating agents operate including, scanning electron microscopy, and in situ fluorescence microscopy. The self-assembly mechanism by which migrating agents operate is described well by depletion forces, which are depend on the geometry of the approaching objects, as well as the migrating agent molecular weight and concentration.

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions.

PubMed

Coari, Kristin M; Martin, Rebecca C; Jain, Kopal; McGown, Linda B

2017-09-01

In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

Nucleotide Selectivity in Abiotic RNA Polymerization Reactions

NASA Astrophysics Data System (ADS)

Coari, Kristin M.; Martin, Rebecca C.; Jain, Kopal; McGown, Linda B.

2017-09-01

In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

Selective deposition and self-assembly of triblock copolymers into matrix arrays for membrane protein production.

PubMed

Andreasson-Ochsner, Mirjam; Fu, Zhikang; May, Sylvia; Xiu, Low Ying; Nallani, Madhavan; Sinner, Eva-Kathrin

2012-01-31

To improve the stability of cell membrane mimics, there has been growing interest in the use of block copolymers. Here, we present an easy approach to create an array of planar polymeric matrices capable of hosting membrane proteins. The array of polymeric matrices was formed by the selective deposition of triblock copolymers onto an array of hydrophilic islands situated within a hydrophobic background. The thickness of these matrices corresponds to the length of a single polymer chain. These polymeric matrices were used to host cell-free expressed membrane proteins, and offers a prototype from which a membrane protein array can be created for diagnostics or drug discovery purposes. © 2011 American Chemical Society

Stress-tuned conductor-polymer composite for use in sensors

DOEpatents

Martin, James E; Read, Douglas H

2013-10-22

A method for making a composite polymeric material with electrical conductivity determined by stress-tuning of the conductor-polymer composite, and sensors made with the stress-tuned conductor-polymer composite made by this method. Stress tuning is achieved by mixing a miscible liquid into the polymer precursor solution or by absorbing into the precursor solution a soluble compound from vapor in contact with the polymer precursor solution. The conductor may or may not be ordered by application of a magnetic field. The composite is formed by polymerization with the stress-tuning agent in the polymer matrix. The stress-tuning agent is removed following polymerization to produce a conductor-polymer composite with a stress field that depends on the amount of stress-tuning agent employed.

Polymeric Nanofibers in Tissue Engineering

PubMed Central

Dahlin, Rebecca L.; Kasper, F. Kurtis

2011-01-01

Polymeric nanofibers can be produced using methods such as electrospinning, phase separation, and self-assembly, and the fiber composition, diameter, alignment, degradation, and mechanical properties can be tailored to the intended application. Nanofibers possess unique advantages for tissue engineering. The small diameter closely matches that of extracellular matrix fibers, and the relatively large surface area is beneficial for cell attachment and bioactive factor loading. This review will update the reader on the aspects of nanofiber fabrication and characterization important to tissue engineering, including control of porous structure, cell infiltration, and fiber degradation. Bioactive factor loading will be discussed with specific relevance to tissue engineering. Finally, applications of polymeric nanofibers in the fields of bone, cartilage, ligament and tendon, cardiovascular, and neural tissue engineering will be reviewed. PMID:21699434

Chemical characterization of selected LDEF polymeric materials

NASA Technical Reports Server (NTRS)

Young, Philip R.; Slemp, Wayne S.

1991-01-01

Chemical characterization of selected polymeric materials which received exposure on the Long Duration Exposure Facility (LDEF) is reported. The specimens examined include silvered fluorinated ethylene propylene Teflon thermal blanket material, polysulfone, epoxy, polyimide matrix resin/graphite fiber reinforced composites, and several high performance polymer films. These specimens came from numerous LDEF locations, and thus received different environmental exposures. The results to date show no significant change at the molecular level in the polymer that survived exposure. Scanning electron and scanning tunneling microscopes show resin loss and a texturing of some specimens which resulted in a change in optical properties. The potential effect of a silicon-containing molecular contamination on these materials is addressed. The possibility of continued post-exposure degradation of some polymeric films is also proposed.

Polymer-based metal nano-coated disposable target for matrix-assisted and matrix-free laser desorption/ionization mass spectrometry.

PubMed

Bugovsky, Stefan; Winkler, Wolfgang; Balika, Werner; Koranda, Manfred; Allmaier, Günter

2016-07-15

The ideal MALDI/LDI mass spectrometry sample target for an axial TOF instrument possesses a variety of properties. Primarily, it should be chemically inert to the sample, i.e. analyte, matrix and solvents, highly planar across the whole target, without any previous chemical contact and provide a uniform surface to facilitate reproducible measurements without artifacts from previous sample or matrix compounds. This can be hard to achieve with a metal target, which has to be extensively cleaned every time after use. Any cleaning step may leave residues behind, may change the surface properties due to the type of cleaning method used or even cause microscopic scratches over time hence altering matrix crystallization behavior. Alternatively, use of disposable targets avoids these problems. As each possesses the same surface they therefore have the potential to replace the conventional full metal targets so commonly employed. Furthermore, low cost single-use targets with high planarity promise an easier compliance with GLP guidelines as they alleviate the problem of low reproducibility due to inconsistent sample/matrix crystallization and changes to the target surface properties. In our tests, polymeric metal nano-coated targets were compared to a stainless steel reference. The polymeric metal nano-coated targets exhibited all the performance characteristics for a MALDI MS sample support, and even surpassed the - in our lab commonly used - reference in some aspects like limit of detection. The target exhibits all necessary features such as electrical conductivity, vacuum, laser and solvent compatibility. Copyright © 2016 Elsevier Inc. All rights reserved.

Polymer functionalized nanocomposites for metals removal from water and wastewater: An overview.

PubMed

Lofrano, Giusy; Carotenuto, Maurizio; Libralato, Giovanni; Domingos, Rute F; Markus, Arjen; Dini, Luciana; Gautam, Ravindra Kumar; Baldantoni, Daniela; Rossi, Marco; Sharma, Sanjay K; Chattopadhyaya, Mahesh Chandra; Giugni, Maurizio; Meric, Sureyya

2016-04-01

Pollution by metal and metalloid ions is one of the most widespread environmental concerns. They are non-biodegradable, and, generally, present high water solubility facilitating their environmental mobilisation interacting with abiotic and biotic components such as adsorption onto natural colloids or even accumulation by living organisms, thus, threatening human health and ecosystems. Therefore, there is a high demand for effective removal treatments of heavy metals, making the application of adsorption materials such as polymer-functionalized nanocomposites (PFNCs), increasingly attractive. PFNCs retain the inherent remarkable surface properties of nanoparticles, while the polymeric support materials provide high stability and processability. These nanoparticle-matrix materials are of great interest for metals and metalloids removal thanks to the functional groups of the polymeric matrixes that provide specific bindings to target pollutants. This review discusses PFNCs synthesis, characterization and performance in adsorption processes as well as the potential environmental risks and perspectives. Copyright © 2016 Elsevier Ltd. All rights reserved.

Plastic scintillators with high loading of one or more metal carboxylates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cherepy, Nerine; Sanner, Robert Dean

In one embodiment, a material includes at least one metal compound incorporated into a polymeric matrix, where the metal compound includes a metal and one or more carboxylate ligands, where at least one of the one or more carboxylate ligands includes a tertiary butyl group, and where the material is optically transparent. In another embodiment, a method includes: processing pulse traces corresponding to light pulses from a scintillator material; and outputting a result of the processing, where the scintillator material comprises at least one metal compound incorporated into a polymeric matrix, the at least one metal compound including a metalmore » and one or more carboxylate ligands, where at least one of the one or more carboxylate ligands has a tertiary butyl group, and where the scintillator material is optically transparent and has an energy resolution at 662 keV of less than about 20%.« less

Physicochemical aspects involved in methotrexate release kinetics from biodegradable spray-dried chitosan microparticles

NASA Astrophysics Data System (ADS)

Mesquita, Philippe C.; Oliveira, Alice R.; Pedrosa, Matheus F. Fernandes; de Oliveira, Anselmo Gomes; da Silva-Júnior, Arnóbio Antônio

2015-06-01

Spray dried methotrexate (MTX) loaded chitosan microparticles were prepared using different drug/copolymer ratios (9%, 18%, 27% and 45% w/w). The physicochemical aspects were assessed in order to select particles that were able to induce a sustained drug release effect. Particles were successfully produced which exhibited desired physicochemical aspects such as spherical shape and high drug loading. XRD and FT-IR analysis demonstrated that drug is not bound to copolymer and is only homogeneously dispersed in an amorphous state into polymeric matrix. Even the particles with higher drug loading levels presented a sustained drug release profile, which were mathematically modeled using adjusted Higuchi model. The drug release occurred predominantly with drug dissolution and diffusion through swollen polymeric matrix, with the slowest release occurring with particles containing 9% of drug, demonstrating an interesting and promising drug delivery system for MTX.

Composite Materials for Low-Temperature Applications

NASA Technical Reports Server (NTRS)

2008-01-01

Composite materials with improved thermal conductivity and good mechanical strength properties should allow for the design and construction of more thermally efficient components (such as pipes and valves) for use in fluid-processing systems. These materials should have wide application in any number of systems, including ground support equipment (GSE), lunar systems, and flight hardware that need reduced heat transfer. Researchers from the Polymer Science and Technology Laboratory and the Cryogenics Laboratory at Kennedy Space Center were able to develop a new series of composite materials that can meet NASA's needs for lightweight materials/composites for use in fluid systems and also expand the plastic-additive markets. With respect to thermal conductivity and physical properties, these materials are excellent alternatives to prior composite materials and can be used in the aerospace, automotive, military, electronics, food-packaging, and textile markets. One specific application of the polymeric composition is for use in tanks, pipes, valves, structural supports, and components for hot or cold fluid-processing systems where heat flow through materials is a problem to be avoided. These materials can also substitute for metals in cryogenic and other low-temperature applications. These organic/inorganic polymeric composite materials were invented with significant reduction in heat transfer properties. Decreases of 20 to 50 percent in thermal conductivity versus that of the unmodified polymer matrix were measured. These novel composite materials also maintain mechanical properties of the unmodified polymer matrix. These composite materials consist of an inorganic additive combined with a thermoplastic polymer material. The intrinsic, low thermal conductivity of the additive is imparted into the thermoplastic, resulting in a significant reduction in heat transfer over that of the base polymer itself, yet maintaining most of the polymer's original properties. Normal polymer processing techniques can turn these composite materials into unique, custom parts for ground support, Shuttle, and Constellation needs. We fabricated test specimens of the composite and base materials for thermal and mechanical characterization and found that the strength of the composite material at nominal-percentage loading remained relatively unchanged from the base material.

Fire- and Heat-Resistant Laminating Resins

NASA Technical Reports Server (NTRS)

Kourtides, Demetrius A.; Mikroyannidis, John A.

1987-01-01

Imide compounds containing phosphourus thermally polymerized. New maleimido- or citraconimido-end-capped monomers, have relatively low melting temperatures, polymerized at moderate temperatures to rigid bisimide resins without elimination of volatiles. Monomers dissolve in such solvents as methyl ethyl ketone, acetone, and tetrahydrofuran, suitable and perferred as "varnish solvents" for composite fabrication. Low melting points of these componds allow use as adhesives without addition of solvents.

Escalation of polymerization in a thermal gradient

PubMed Central

Mast, Christof B.; Schink, Severin; Gerland, Ulrich; Braun, Dieter

2013-01-01

For the emergence of early life, the formation of biopolymers such as RNA is essential. However, the addition of nucleotide monomers to existing oligonucleotides requires millimolar concentrations. Even in such optimistic settings, no polymerization of RNA longer than about 20 bases could be demonstrated. How then could self-replicating ribozymes appear, for which recent experiments suggest a minimal length of 200 nt? Here, we demonstrate a mechanism to bridge this gap: the escalated polymerization of nucleotides by a spatially confined thermal gradient. The gradient accumulates monomers by thermophoresis and convection while retaining longer polymers exponentially better. Polymerization and accumulation become mutually self-enhancing and result in a hyperexponential escalation of polymer length. We describe this escalation theoretically under the conservative assumption of reversible polymerization. Taking into account the separately measured thermophoretic properties of RNA, we extrapolate the results for primordial RNA polymerization inside a temperature gradient in pores or fissures of rocks. With a dilute, nanomolar concentration of monomers the model predicts that a pore length of 5 cm and a temperature difference of 10 K suffice to polymerize 200-mers of RNA in micromolar concentrations. The probability to generate these long RNAs is raised by a factor of >10600 compared with polymerization in a physical equilibrium. We experimentally validate the theory with the reversible polymerization of DNA blocks in a laser-driven thermal trap. The results confirm that a thermal gradient can significantly enlarge the available sequence space for the emergence of catalytically active polymers. PMID:23630280

Cell-micropatterning by micromolding in capillary technique based on UV polymerization

NASA Astrophysics Data System (ADS)

Park, Min J.; Choi, Won M.; Park, O. O.

2006-01-01

Although optical lithography or photolithography is one of the most well-established techniques for micro, nano-fabrication, its usage with proteins and cells is restricted by steps that must be carried out in harsh organic solvents. Here, we present simple methods for cell-micropatterning using poly(dimethylsiloxane) (PDMS) as a mold. Cell non-adhesive surface or nonfouling surface providing a physico-chemical barrier to cell attachment was introduced for biomaterial pattering, where cells fail to interact with the surface over desired periods of time determined by each application. Poly(ethylene glycol) (PEG) was selected as nonfouling material to inhibit protein adsorption from biological media. The fouling resistance of PEG polymer is often explained by a steric repulsion interaction, resulting from the compression of PEG chains as proteins approach the surface. We also chose fibronectin to direct cell attachment because it is an extracellular matrix protein that is involved in the adhesion and spreading of anchorage-dependent cells. In our experiment, we propose two methods by application of micromolding in capillary (MIMIC) method based on UV polymerization to obtain a surface of alternating PEG and fibronectin. First to fabricate PEG microstructure via MIMIC method, a pre-patterned PDMS mold is placed on a desired substrate, and then the relief structure in the mold forms a network of empty channels. A drop of ethylene glycol monomer solution containing initiator for UV polymerization is placed at the open ends of the network of channels, which is then polymerized by exposure to UV light at room temperature. Once PEG microstructure is fabricated, incubation of the patterned surface in a fibronectin-containing solution allows back-filling of only the bare regions with fibronectin via adsorption. In the alternative method, a substrate is first incubated in a fibronectin-containing solution, leading to the adsorption of fibronectin over the entire surface, and the fibronectin-adsorbed substrate is then micropatterned with the PEG by MIMIC based on UV polymerization. Both methods create reproducible alternating PEG and fibronectin patterns applicable to cell-surface interactions on the microscale.

Preparation and characterization of polyaniline-containing Na-AlMCM-41 as composite material with semiconductor behavior.

PubMed

Anunziata, Oscar A; Gómez Costa, Marcos B; Sánchez, Rodolfo D

2005-12-15

Composite material formed from a mesoporous aluminosilicate, Na-AlMCM-41, with conducting polyaniline (PANI) has been synthesized by an in situ polymerization technique. Studies of aniline adsorption over mesoporous Na-AlMCM-41 synthesized in our laboratory allowed us to find the modes in which aniline interacts with the active sites of Na-AlMCM-41. In order to obtain the best reaction conditions to polymerize aniline onto Na-AlMCM-41, aniline was first polymerized to produce pure PANI. Hence, the oxidative in situ polymerization was carried out by two procedures, differing in the polymerization time and in static or stirring conditions. Studies of infrared spectroscopy and UV-vis spectroscopy indicated that higher polymerization time and static conditions allowed us to obtain mainly polyaniline in emeraldine form on the host. The N(2) isotherm of the polyaniline/Na-AlMCM-41 composite (PANI/MCM) indicated that the shape was similar to that of MCM, but the shift to saturation transition to lower partial pressure shows that the channels are occupied by PANI and they are now narrowed. The thermal properties of PANI, Na-AlMCM-41, and composite were investigated by TGA analyses and we found that the polymer shows higher thermal stability when it is forming the composite. Scanning electron microscopy indicated that PANI is not on the outer surface of the host. Conductivity studies show that PANI/Na-AlMCM-41 exhibits semiconductor behavior at room temperature and its conductivity was 7.0 x 10(-5) S/cm, smaller than that of pure polyaniline. PANI/Na-AlMCM-41 conductivity shows an increase as temperature increases. Magnetic measurements at room temperature confirmed that the composite has paramagnetic behavior; at lower temperatures the composite became diamagnetic.

Evaporation rate and vapor pressure of selected polymeric lubricating oils.

NASA Technical Reports Server (NTRS)

Gardos, M. N.

1973-01-01

A recently developed ultrahigh-vacuum quartz spring mass sorption microbalance has been utilized to measure the evaporation rates of several low-volatility polymeric lubricating oils at various temperatures. The evaporation rates are used to calculate the vapor pressures by the Langmuir equation. A method is presented to accurately estimate extended temperature range evaporation rate and vapor pressure data for polymeric oils, incorporating appropriate corrections for the increases in molecular weight and the change in volatility of the progressively evaporating polymer fractions. The logarithms of the calculated data appear to follow linear relationships within the test temperature ranges, when plotted versus 1000/T. These functions and the observed effusion characteristics of the fluids on progressive volatilization are useful in estimating evaporation rate and vapor pressure changes on evaporative depletion.

Comparison of In Situ Polymerization and Solution-Dispersion Techniques in the Preparation of Polyimide/Montmorillonite (MMT) Nanocomposites

PubMed Central

Ahmad, Mansor Bin; Gharayebi, Yadollah; Salit, Mohd. Sapuan; Hussein, Mohd. Zobir; Shameli, Kamyar

2011-01-01

In this paper, Polyimide/Montmorillonite Nanocomposites (PI/MMT NCs), based on aromatic diamine (4-Aminophenyl sulfone) (APS) and aromatic dianhydride (3,3′,4,4′-benzophenonetetracarboxylic dianhydride) (BTDA) were prepared using in situ polymerization and solution-dispersion techniques. The prepared PI/MMT NCs films were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The XRD results showed that at the content of 1.0 wt % Organo Montmorillonite (OMMT) for two techniques and 3.0 wt % OMMT for the in situ polymerization technique, the OMMT was well-intercalated, exfoliated and dispersed into polyimide matrix. The OMMT agglomerated when its amount exceeded 10 wt % and 3.0 wt % for solution-dispersion and in situ polymerization techniques respectively. These results were confirmed by the TEM images of the prepared PI/MMT NCs. The TGA thermograms indicated that thermal stability of prepared PI/MMT NCs were increased with the increase of loading that, the effect is higher for the samples prepared by in situ polymerization technique. PMID:22016643

Comparison of in situ polymerization and solution-dispersion techniques in the preparation of Polyimide/Montmorillonite (MMT) Nanocomposites.

PubMed

Ahmad, Mansor Bin; Gharayebi, Yadollah; Salit, Mohd Sapuan; Hussein, Mohd Zobir; Shameli, Kamyar

2011-01-01

In this paper, Polyimide/Montmorillonite Nanocomposites (PI/MMT NCs), based on aromatic diamine (4-Aminophenyl sulfone) (APS) and aromatic dianhydride (3,3',4,4'-benzophenonetetracarboxylic dianhydride) (BTDA) were prepared using in situ polymerization and solution-dispersion techniques. The prepared PI/MMT NCs films were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and thermogravimetric analysis (TGA). The XRD results showed that at the content of 1.0 wt % Organo Montmorillonite (OMMT) for two techniques and 3.0 wt % OMMT for the in situ polymerization technique, the OMMT was well-intercalated, exfoliated and dispersed into polyimide matrix. The OMMT agglomerated when its amount exceeded 10 wt % and 3.0 wt % for solution-dispersion and in situ polymerization techniques respectively. These results were confirmed by the TEM images of the prepared PI/MMT NCs. The TGA thermograms indicated that thermal stability of prepared PI/MMT NCs were increased with the increase of loading that, the effect is higher for the samples prepared by in situ polymerization technique.

Composite material pedestrian bridge for the Port of Bilbao

NASA Astrophysics Data System (ADS)

Gorrochategui, I.; Manteca, C.; Yedra, A.; Miguel, R.; del Valle, F. J.

2012-09-01

Composite materials in comparison to traditional ones, steel and concrete, present advantages in civil works construction: lower weight, higher corrosion resistance (especially in the marine environment), and ease of installation. On the other hand, fabrication costs are generally higher. This is the reason why this technology is not widely used. This work illustrates the process followed for the design, fabrication and installation of a composite material pedestrian bridge in the Port of Bilbao (Northern Spain). In order to reduce the price of the bridge, the use of low cost materials was considered, therefore polyester resin was selected as the polymeric matrix, and glass fibres as reinforcement. Two material choices were studied. Currently in the market there is high availability of carbon nanoparticles: carbon nanotubes (CNT) and carbon nanofibres (CNF), so it was decided to add this kind of nanoparticles to the reference material with the objective of improving its mechanical properties. The main challenge was to transfer the CNT and CNF excellent properties to the polymeric matrix. This requires dispersing the nanoreinforcements as individual particles in the polymeric matrix to avoid agglomerates. For this reason, an advanced high shear forces dispersion technique (called "three roll mills") was studied and implemented. Also surface functionalization of the nanoreinforcements by chemical treatment was carried out. Herein, a comparison is performed between both materials studied, the explanation of the employment of the reference material (without nanoreinforcement) as the one used in the fabrication of the pedestrian bridge is justified and, finally, the main characteristics of the final design of the structural element are described.

Using solvent-free sample preparation to promote protonation of poly(ethylene oxide)s with labile end-groups in matrix-assisted laser desorption/ionisation.

PubMed

Mazarin, Michael; Phan, Trang N T; Charles, Laurence

2008-12-01

Protonation is usually required to observe intact ions during matrix-assisted laser desorption/ionization (MALDI) of polymers containing fragile end-groups while cation adduction induces chain-end degradation. These polymers, generally obtained via living free radical polymerization techniques, are terminated with a functionality in which a bond is prone to homolytic cleavage, as required by the polymerization process. A solvent-free sample preparation method was used here to avoid salt contaminant from the solvent traditionally used in the dried-droplet MALDI procedure. Solvent-based and solvent-free sample preparations were compared for a series of three poly(ethylene oxide) polymers functionalized with a labile end-group in a nitroxide-mediated polymerization reaction, using 2,4,6-trihydroxyacetophenone (THAP) as the matrix without any added salt. Intact oligomer ions could only be produced as protonated molecules in solvent-free MALDI while sodium adducts of degraded polymers were formed from the dried-droplet samples. Although MALDI analysis was performed at the laser threshold, fragmentation of protonated macromolecules was still observed to occur. However, in contrast to sodiated molecules, dissociation of protonated oligomers does not involve the labile C--ON bond of the end-group. As the macromolecule size increased, protonation appeared to be less efficient and sodium adduction became the dominant ionization process, although no sodium salt was added in the preparation. Formation of sodiated degraded macromolecules would be dictated by increasing cation affinity as the size of the oligomers increases and would reveal the presence of salts at trace levels in the MALDI samples.

A robust Ni(II) α-diimine catalyst for high temperature ethylene polymerization.

PubMed

Rhinehart, Jennifer L; Brown, Lauren A; Long, Brian K

2013-11-06

Sterically demanding Ni(II) α-diimine precatalysts were synthesized utilizing 2,6-bis(diphenylmethyl)-4-methyl aniline. When activated with methylaluminoxane, the catalyst NiBr2(ArN═C(Me)-C(Me)═NAr) (Ar = 2,6 bis(diphenylmethyl)-4-methylbenzene) was highly active, produced well-defined polyethylene at temperatures up to 100 °C (Mw/Mn = 1.09-1.46), and demonstrated remarkable thermal stability at temperatures appropriate for industrially used gas-phase polymerizations (80-100 °C).

Recent Development of Flax Fibres and Their Reinforced Composites Based on Different Polymeric Matrices

PubMed Central

Zhu, Jinchun; Zhu, Huijun; Njuguna, James; Abhyankar, Hrushikesh

2013-01-01

This work describes flax fibre reinforced polymeric composites with recent developments. The properties of flax fibres, as well as advanced fibre treatments such as mercerization, silane treatment, acylation, peroxide treatment and coatings for the enhancement of flax/matrix incompatibility are presented. The characteristic properties and characterizations of flax composites on various polymers including polypropylene (PP) and polylactic acid, epoxy, bio-epoxy and bio-phenolic resin are discussed. A brief overview is also given on the recent nanotechnology applied in flax composites. PMID:28788383

Polymerization of Fluoroalkyl Polyhedral Oligomeric Silsesquioxane (F-POSS) Macromers

DTIC Science & Technology

2012-12-01

mm Methanol Octane Methylene Iodide Water Superhydrophobic /oleophilic dip-coated fabric Tuteja et al, Science, 2007, 318, 1618 Superamphiphobic...robust superhydrophobic /oleophobic/omniphobic surfaces • Via covalently attached F-POSS to substrate (surface, nanoparticle, polymer matrix) – Effects

Comparison of temperature change among different adhesive resin cement during polymerization process.

PubMed

Alkurt, Murat; Duymus, Zeynep Yesil; Gundogdu, Mustafa; Karadas, Muhammet

2017-01-01

The aim of this study was to assess the intra-pulpal temperature changes in adhesive resin cements during polymerization. Dentin surface was prepared with extracted human mandibular third molars. Adhesive resin cements (Panavia F 2.0, Panavia SA, and RelyX U200) were applied to the dentin surface and polymerized under IPS e.max Press restoration. K-type thermocouple wire was positioned in the pulpal chamber to measure temperature change ( n = 7). The temperature data were recorded (0.0001 sensible) and stored on a computer every 0.1 second for sixteen minutes. Differences between the baseline temperature and temperatures of various time points (2, 4, 6, 8, 10, 12, 14, and 16 minute) were determined and mean temperature changes were calculated. At various time intervals, the differences in temperature values among the adhesive resin cements were analyzed by two-way ANOVA and post-hoc Tukey honestly test (α = 0.05). Significant differences were found among the time points and resin cements ( P < 0.05). Temperature values of the Pan SA group were significantly higher than Pan F and RelyX ( P < 0.05). Result of the study on self-adhesive and self-etch adhesive resin cements exhibited a safety intra-pulpal temperature change.

E-Beam Processing of Polymer Matrix Composites for Multifunctional Radiation Shielding

NASA Technical Reports Server (NTRS)

Hou, Tan-Hung; Wilson, John W.; Jensen, Brian J.; Thibeault, Sheila A.; Chang, Chie K.; Kiefer, Richard L.

2005-01-01

Aliphatic polymers were identified as optimum radiation shielding polymeric materials for building multifunctional structural elements for in-space habitats. Conceptual damage tolerant configurations of polyolefins have been proposed, but many manufacturing issues relied on methods and materials which have sub-optimal radiation shielding characteristics (for example, epoxy matrix and adhesives). In the present approach, we shall investigate e-beam processing technologies for inclusion of high-strength aliphatic polymer reinforcement structures into a highly cross-linked polyolefin matrix. This paper reports the baseline thermo-mechanical properties of low density polyethylene and highly crystallized polyethylene.

Characterization of selected LDEF polymer matrix resin composite materials

NASA Technical Reports Server (NTRS)

Young, Philip R.; Slemp, Wayne S.; Witte, William G., Jr.; Shen, James Y.

1991-01-01

The characterization of selected graphite fiber reinforced epoxy (934 and 5208) and polysulfone (P1700) matrix resin composite materials which received 5 years and 10 months of exposure to the LEO environment on the Long Duration Exposure Facility is reported. Resin loss and a decrease in mechanical performance as well as dramatic visual effects were observed. However, chemical characterization including infrared, thermal, and selected solution property measurements showed that the molecular structure of the polymeric matrix had not changed significantly in response to this exposure. The potential effect of a silicon-containing molecular contamination of these specimens is addressed.

Improvement of mechanical properties of polymeric composites: Experimental methods and new systems

NASA Astrophysics Data System (ADS)

Nguyen, Felix Nhanchau

Filler- (e.g., particulate or fiber) reinforced structural polymers or polymeric composites have changed the way things are made. Today, they are found, for example, in air/ground transportation vehicles, sporting goods, ballistic barrier applications and weapons, electronic packaging, musical instruments, fashion items, and more. As the demand increases, so does the desire to have not only well balanced mechanical properties, but also light weight and low cost. This leads to a constant search for novel constituents and additives, new fabrication methods and analytical techniques. To achieve new or improved composite materials requires more than the identification of the right reinforcements to be used with the right polymer matrix at the right loading. Also, an optimized adhesion between the two phases and a toughened matrix system are needed. This calls for new methods to predict, modify and assess the level of adhesion, and new developments in matrix tougheners to minimize compromises in other mechanical/thermal properties. Furthermore, structural optimization, associated with fabrication (e.g., avoidance of fiber-fiber touching or particle aggregation), and sometimes special properties, such as electrical conductivity or magnetic susceptibility are necessary. Finally, the composite system's durability, often under hostile conditions, is generally mandatory. The present study researches new predictive and experimental methods for optimizing and characterizing filler-matrix adhesion and develops a new type of epoxy tougheners. Specifically, (1) a simple thermodynamic parameter evaluated by UNIFAC is applied successfully to screen out candidate adhesion promoters, which is necessary for optimization of the physio-chemical interactions between the two phases; (2) an optical-acoustical mechanical test assisted with an acoustic emission technique is developed to de-convolute filler debonding/delamination among many other micro failure events, and (3) novel core (thermoplastic)-shell (dendrimer) nanoparticles are synthesized and incorporated in epoxy to enhance both stiffness and the polymer's fracture toughness or resistance to crack growth. This unique dendrimer has the possibility of acting both as an adhesion promoter and filler spacer, when applied to the filler surface, and as a matrix enhancer, when combined with other materials, with the unique ability to improve mechanical/thermal/electrical properties. These developments should help in the creation of the next generation of polymeric composites.

One-step synthesis and characterization of polyaniline nanofiber/silver nanoparticle composite networks as antibacterial agents.

PubMed

Poyraz, Selcuk; Cerkez, Idris; Huang, Tung Shi; Liu, Zhen; Kang, Litao; Luo, Jujie; Zhang, Xinyu

2014-11-26

Through a facile and effective seeding polymerization reaction via a one-step redox/complexation process, which took place in aqueous medium at ambient temperature, silver nanoparticles (Ag NPs) embedded polyaniline nanofiber (PANI NF) networks were synthesized as antibacterial agents. During the reaction, not only NF morphology formation of the resulting conducting polymers (CPs) but also amplification of the aqueous silver nitrate (AgNO3) solutions' oxidative potentials were managed by vanadium pentoxide (V2O5) sol-gel nanofibers, which acted as well-known nanofibrous seeding agents and the auxiliary oxidative agent at the same time. The PANI/Ag nanocomposites were proven to exhibit excellent antibacterial property against both Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. Antibacterial property performance and average life span of the nanocomposite network were optimized through the homogeneous distribution/embedment of Ag NPs within one-dimensional (1-D) PANI NF matrix. The antibacterial efficacy tests and nanocomposite material characterization results further indicated that the sole components of PANI/Ag have a synergistic effect to each other in terms of antibacterial property. Thus, this well-known catalytic seeding approach via a one-step oxidative polymerization reaction can be considered as a general methodology and a substantial fabrication tool to synthesize Ag NP decorated nanofibrillar PANI networks as advanced antibacterial agents.

Structure and magnetic properties of Ni-poly(p-xylylene) nanocomposites synthesized by vapor deposition polymerization

NASA Astrophysics Data System (ADS)

Ozerin, Sergei A.; Vdovichenko, Artem Yu.; Streltsov, Dmitry R.; Davydov, Alexander B.; Orekhov, Anton S.; Vasiliev, Alexander L.; Zubavichus, Yan V.; Grigoriev, Evgenii I.; Zavyalov, Sergei A.; Oveshnikov, Leonid N.; Aronzon, Boris A.; Chvalun, Sergei N.

2017-12-01

The relationship between structure, electrical and magnetic properties of thin poly(p-xylylene) - nickel nanocomposite films with Ni concentrations from 5 to 30 vol% was studied. It was found that metal concentration strongly affects size and oxidation state of the nanoparticles and composites morphology. At nickel concentration below 5 vol% the nanoparticles are oxidized to NiO and homogeneously distributed within fine-grained polymer matrix. An increase of Ni concentration up to 10 vol% results in the development of coarse-grained morphology with preferable localization of the nanoparticles at the boundaries of polymeric grains. And finally, in the composite films with nickel concentration above 20 vol%, the fine-grained morphology is observed again, but the nanoparticles are mainly metallic. Effect of the filler content on electrical and magnetic properties of the nanocomposites was elucidated showing that they are determined by percolation phenomenon with the threshold value of about 10 vol%. The well-pronounced magnetic hysteresis as well as ferromagnetic ordering were observed at Ni content above the percolation threshold. The diagrams of magnetic properties of these composites as a function of composition and temperature were elaborated. It was demonstrated that film annealing can be used to control magnetic properties of the composites and strongly enhance magnetoresistance.

Dually Fluorescent Sensing of pH and Dissolved Oxygen Using a Membrane Made from Polymerizable Sensing Monomers.

PubMed

Tian, Yanqing; Shumway, Bradley R; Youngbull, A Cody; Li, Yongzhong; Jen, Alex K-Y; Johnson, Roger H; Meldrum, Deirdre R

2010-06-03

Using a thermal polymerization approach and polymerizable pH and oxygen sensing monomers with green and red emission spectra, respectively, new pH, oxygen, and their dual sensing membranes were prepared using poly(2-hydroxyethyl methacrylate)-co-poly(acrylamide) as a matrix. The sensors were grafted on acrylate-modified quartz glass and characterized under different pH values, oxygen concentrations, ion strengths, temperatures and cell culture media. The pH and oxygen sensors were excited using the same excitation wavelength and exhibited well-separated emission spectra. The pH-sensing films showed good response over the pH range 5.5 to 8.5, corresponding to pK(a) values in the biologically-relevant range between 6.9 and 7.1. The oxygen-sensing films exhibited linear Stern-Volmer quenching responses to dissolved oxygen. As the sensing membranes were prepared using thermally initiated polymerization of sensing moiety-containing monomers, no leaching of the sensors from the membranes to buffers or medium was observed. This advantageous characteristic accounts in part for the sensors' biocompatibility without apparent toxicity to HeLa cells after 40 hours incubation. The dual-sensing membrane was used to measure pH and dissolved oxygen simultaneously. The measured results correlated with the set-point values.

Well-dispersed cellulose nanocrystals in hydrophobic polymers by in situ polymerization for synthesizing highly reinforced bio-nanocomposites.

PubMed

Geng, Shiyu; Wei, Jiayuan; Aitomäki, Yvonne; Noël, Maxime; Oksman, Kristiina

2018-04-20

In nanocomposites, dispersing hydrophilic nanomaterials in a hydrophobic matrix using simple and environmentally friendly methods remains challenging. Herein, we report a method based on in situ polymerization to synthesize nanocomposites of well-dispersed cellulose nanocrystals (CNCs) and poly(vinyl acetate) (PVAc). We have also shown that by blending this PVAc/CNC nanocomposite with poly(lactic acid) (PLA), a good dispersion of the CNCs can be reached in PLA. The outstanding dispersion of CNCs in both PVAc and PLA/PVAc matrices was shown by different microscopy techniques and was further supported by the mechanical and rheological properties of the composites. The in situ PVAc/CNC nanocomposites exhibit enhanced mechanical properties compared to the materials produced by mechanical mixing, and a theoretical model based on the interphase effect and dispersion that reflects this behavior was developed. Comparison of the rheological and thermal behaviors of the mixed and in situ PVAc/CNC also confirmed the great improvement in the dispersion of nanocellulose in the latter. Furthermore, a synergistic effect was observed with only 0.1 wt% CNCs when the in situ PVAc/CNC was blended with PLA, as demonstrated by significant increases in elastic modulus, yield strength, elongation to break and glass transition temperature compared to the PLA/PVAc only material.

Conductivity enhancement of surface-polymerized polyaniline films via control of processing conditions

NASA Astrophysics Data System (ADS)

Park, Chung Hyoi; Jang, Sung Kyu; Kim, Felix Sunjoo

2018-01-01

We investigate a fast and facile approach for the simultaneous synthesis and coating of conducting polyaniline (PANI) onto a substrate and the effects of processing conditions on the electrical properties of the fabricated films. Simultaneous polymerizing and depositing on the substrate forms a thin film with the average thickness of 300 nm and sheet resistance of 304 Ω/sq. Deposition conditions such as polymerization time (3-240 min), temperature (-10 to 40 °C), concentrations of monomer and oxidant (0.1-0.9 M), and type of washing solvents (acetone, water, and/or HCl solution) affect the film thickness, doping state, absorption characteristics, and solid-state nanoscale morphology, therefore affecting the electrical conductivity. Among the conditions, the surface-polymerized PANI film deposited at room temperature with acetone washing showed the highest conductivity of 22.2 S/cm.

Method for preparing dioxyheterocycle-based electrochromic polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reynolds, John R.; Estrada, Leandro; Deininger, James

A method for preparing a conjugated polymer involves a DHAP polymerization of a 3,4-dioxythiophene, 3,4-dioxyfuran, or 3,4-dioxypyrrole and, optionally, at least one second conjugated monomer in the presence of a Pd or Ni comprising catalyst, an aprotic solvent, a carboxylic acid at a temperature in excess of 120.degree. C. At least one of the monomers is substituted with hydrogen reactive functionalities and at least one of the monomers is substituted with a Cl, Br, and/or I. The polymerization can be carried out at temperature of 140.degree. C. or more, and the DHAP polymerization can be carried out without a phosphinemore » ligand or a phase transfer agent. The resulting polymer can display dispersity less than 2 and have a degree of polymerization in excess of 10.« less

Altered native stability is the dominant basis for susceptibility of α1-antitrypsin mutants to polymerization

PubMed Central

Irving, James A.; Haq, Imran; Dickens, Jennifer A.; Faull, Sarah V.; Lomas, David A.

2014-01-01

Serpins are protease inhibitors whose most stable state is achieved upon transition of a central 5-stranded β-sheet to a 6-stranded form. Mutations, low pH, denaturants and elevated temperatures promote this transition, which can result in a growing polymer chain of inactive molecules. Different types of polymer are possible, but, experimentally only heat has been shown to generate polymers in vitro consistent with ex vivo pathological specimens. Many mutations that alter the rate of heat-induced polymerization have been described, but interpretation is problematic because discrimination is lacking between the effect of global changes in native stability and specific effects on structural mechanism. We show that the temperature midpoint (Tm) of thermal denaturation reflects the transition of α1-antitrypsin to the polymerization intermediate, and determine the relationship with fixed-temperature polymerization half-times (t0.5) in the presence of stabilizing additives [TMAO (trimethylamine N-oxide), sucrose and sodium sulfate], point mutations and disulfide bonds. Combined with a retrospective analysis of 31 mutants characterized in the literature, the results of the present study show that global changes to native state stability are the predominant basis for the effects of mutations and osmolytes on heat-induced polymerization, summarized by the equation: ln(t0.5,mutant/t0.5,wild-type)=0.34×ΔTm. It is deviations from this relationship that hold key information about the polymerization process. PMID:24552432

An Acrylonitrile–Butadiene–Lignin Renewable Skin with Programmable and Switchable Electrical Conductivity for Stress/Strain-Sensing Applications

DOE PAGES

Nguyen, Ngoc A.; Meek, Kelly M.; Bowland, Christopher C.; ...

2017-12-28

We report an approach for programming electrical conductivity of a bio-based leathery skin devised with a layer of 60 nm metallic nanoparticles. Lignin-based renewable shape-memory materials were made, for the first time, to program and restore the materials’ electrical conductivity after repeated deformation up to 100% strain amplitude, at a temperature 60–115 °C above the glass transition temperature (T g) of the rubbery matrix. We cross-linked lignin macromolecules with an acrylonitrile–butadiene rubbery melt in high quantities ranging from 40 to 60 wt % and processed the resulting thermoplastics into thin films. Chemical and physical networks within the polymeric materials significantlymore » enhanced key characteristics such as mechanical stiffness, strain fixity, and temperature-stimulated recovery of shape. The branched structures of the guaiacylpropane-dominant softwood lignin significantly improve the rubber’s T g and produced a film with stored and recoverable elastic work density that was an order of magnitude greater than those of the neat rubber and of samples made with syringylpropane-rich hardwood lignin. The devices could exhibit switching of conductivity before and after shape recovery.« less

An Acrylonitrile–Butadiene–Lignin Renewable Skin with Programmable and Switchable Electrical Conductivity for Stress/Strain-Sensing Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Ngoc A.; Meek, Kelly M.; Bowland, Christopher C.

We report an approach for programming electrical conductivity of a bio-based leathery skin devised with a layer of 60 nm metallic nanoparticles. Lignin-based renewable shape-memory materials were made, for the first time, to program and restore the materials’ electrical conductivity after repeated deformation up to 100% strain amplitude, at a temperature 60–115 °C above the glass transition temperature (T g) of the rubbery matrix. We cross-linked lignin macromolecules with an acrylonitrile–butadiene rubbery melt in high quantities ranging from 40 to 60 wt % and processed the resulting thermoplastics into thin films. Chemical and physical networks within the polymeric materials significantlymore » enhanced key characteristics such as mechanical stiffness, strain fixity, and temperature-stimulated recovery of shape. The branched structures of the guaiacylpropane-dominant softwood lignin significantly improve the rubber’s T g and produced a film with stored and recoverable elastic work density that was an order of magnitude greater than those of the neat rubber and of samples made with syringylpropane-rich hardwood lignin. The devices could exhibit switching of conductivity before and after shape recovery.« less

Mechanochemical Synthesis of Pharmaceutical Cocrystal Suspensions via Hot Melt Extrusion: Feasibility Studies and Physicochemical Characterization.

PubMed

Li, Shu; Yu, Tao; Tian, Yiwei; McCoy, Colin P; Jones, David S; Andrews, Gavin P

2016-09-06

Engineered cocrystals offer an alternative solid drug form with tailored physicochemical properties. Interestingly, although cocrystals provide many new possibilities, they also present new challenges, particularly in regard to their design and large-scale manufacture. Current literature has primarily focused on the preparation and characterization of novel cocrystals typically containing only the drug and coformer, leaving the subsequent formulation less explored. In this paper we propose, for the first time, the use of hot melt extrusion for the mechanochemical synthesis of pharmaceutical cocrystals in the presence of a meltable binder. In this approach, we examine excipients that are amenable to hot melt extrusion, forming a suspension of cocrystal particulates embedded in a pharmaceutical matrix. Using ibuprofen and isonicotinamide as a model cocrystal reagent pair, formulations extruded with a small molecular matrix carrier (xylitol) were examined to be intimate mixtures wherein the newly formed cocrystal particulates were physically suspended in a matrix. With respect to formulations extruded using polymeric carriers (Soluplus and Eudragit EPO, respectively), however, there was no evidence within PXRD patterns of either crystalline ibuprofen or the cocrystal. Importantly, it was established in this study that an appropriate carrier for a cocrystal reagent pair during HME processing should satisfy certain criteria including limited interaction with parent reagents and cocrystal product, processing temperature sufficiently lower than the onset of cocrystal Tm, low melt viscosity, and rapid solidification upon cooling.

Influence of carbon nanoparticles/epoxy matrix interaction on mechanical, electrical and transport properties of structural advanced materials

NASA Astrophysics Data System (ADS)

Guadagno, Liberata; Naddeo, Carlo; Raimondo, Marialuigia; Barra, Giuseppina; Vertuccio, Luigi; Russo, Salvatore; Lafdi, Khalid; Tucci, Vincenzo; Spinelli, Giovanni; Lamberti, Patrizia

2017-03-01

The focus of this study is to design new nano-modified epoxy formulations using carbon nanofillers, such as carbon nanotubes, carbon nanofibers and graphene-based nanoparticles (CpEG), that reduce the moisture content and provide additional functional performance. The chemical structure of epoxy mixture, using a non-stoichiometric amount of hardener, exhibits unique properties in regard to the water sorption for which the equilibrium concentration of water (C eq) is reduced up to a maximum of 30%. This result, which is very relevant for several industrial applications (aeronautical, shipbuilding industries, wind turbine blades, etc), is due to a strong reduction of the polar groups and/or sites responsible to bond water molecules. All nanofillers are responsible of a second phase at lower glass transition temperature (Tg). Compared with other carbon nanofillers, functionalized graphene-based nanoparticles exhibit the best performance in the multifunctionality. The lowest moisture content, the high performance in the mechanical properties, the low electrical percolation threshold (EPT) have been all ascribed to particular arrangements of the functionalized graphene sheets embedded in the polymeric matrix. Exfoliation degree and edge carboxylated groups are responsible of self-assembled architectures which entrap part of the resin fraction hindering the interaction of water molecules with the polar sites of the resin, also favouring the EPT paths and the attractive/covalent interactions with the matrix.

Influence of carbon nanoparticles/epoxy matrix interaction on mechanical, electrical and transport properties of structural advanced materials.

PubMed

Guadagno, Liberata; Naddeo, Carlo; Raimondo, Marialuigia; Barra, Giuseppina; Vertuccio, Luigi; Russo, Salvatore; Lafdi, Khalid; Tucci, Vincenzo; Spinelli, Giovanni; Lamberti, Patrizia

2017-03-03

The focus of this study is to design new nano-modified epoxy formulations using carbon nanofillers, such as carbon nanotubes, carbon nanofibers and graphene-based nanoparticles (CpEG), that reduce the moisture content and provide additional functional performance. The chemical structure of epoxy mixture, using a non-stoichiometric amount of hardener, exhibits unique properties in regard to the water sorption for which the equilibrium concentration of water (C eq ) is reduced up to a maximum of 30%. This result, which is very relevant for several industrial applications (aeronautical, shipbuilding industries, wind turbine blades, etc), is due to a strong reduction of the polar groups and/or sites responsible to bond water molecules. All nanofillers are responsible of a second phase at lower glass transition temperature (Tg). Compared with other carbon nanofillers, functionalized graphene-based nanoparticles exhibit the best performance in the multifunctionality. The lowest moisture content, the high performance in the mechanical properties, the low electrical percolation threshold (EPT) have been all ascribed to particular arrangements of the functionalized graphene sheets embedded in the polymeric matrix. Exfoliation degree and edge carboxylated groups are responsible of self-assembled architectures which entrap part of the resin fraction hindering the interaction of water molecules with the polar sites of the resin, also favouring the EPT paths and the attractive/covalent interactions with the matrix.

Scalable-manufactured randomized glass-polymer hybrid metamaterial for daytime radiative cooling

NASA Astrophysics Data System (ADS)

Zhai, Yao; Ma, Yaoguang; David, Sabrina N.; Zhao, Dongliang; Lou, Runnan; Tan, Gang; Yang, Ronggui; Yin, Xiaobo

2017-03-01

Passive radiative cooling draws heat from surfaces and radiates it into space as infrared radiation to which the atmosphere is transparent. However, the energy density mismatch between solar irradiance and the low infrared radiation flux from a near-ambient-temperature surface requires materials that strongly emit thermal energy and barely absorb sunlight. We embedded resonant polar dielectric microspheres randomly in a polymeric matrix, resulting in a metamaterial that is fully transparent to the solar spectrum while having an infrared emissivity greater than 0.93 across the atmospheric window. When backed with a silver coating, the metamaterial shows a noontime radiative cooling power of 93 watts per square meter under direct sunshine. More critically, we demonstrated high-throughput, economical roll-to-roll manufacturing of the metamaterial, which is vital for promoting radiative cooling as a viable energy technology.

Multiscale Analysis of the Residual Stresses Occurring During Curing and Cooling of Thick-Wall Cross-Ply Filament-Wound Cylinders

NASA Astrophysics Data System (ADS)

Memarianfard, H.; Turusov, R. A.

2017-11-01

A nonlinear numerical multiscale analysis to predict the residual shrinkage and thermal stresses arising during curing and cooling of thickwall cross-ply filament-wound cylinders of a reinforced polymer is performed at macro- and microscales using the representative volume element (RVE) of the composite. The mechanical behavior of the polymeric matrix is described by a nonlinear viscoelastic model with account of chemical shrinkage. The fiber material is considered elastic, isotropic, and temperature-independent. The maximum residual macrostresses arising during manufacture of the cylinders were calculated. The fields of residual microstresses in the RVE in three different zones across the thickness of the cylinders were found. Results of the microscale analysis showed that microstresses in some zones of RVE were several times higher than macrostresses in these areas.

Osteoconductive Amine-Functionalized Graphene-Poly(methyl methacrylate) Bone Cement Composite with Controlled Exothermic Polymerization.

PubMed

Sharma, Rakesh; Kapusetti, Govinda; Bhong, Sayali Yashwant; Roy, Partha; Singh, Santosh Kumar; Singh, Shikha; Balavigneswaran, Chelladurai Karthikeyan; Mahato, Kaushal Kumar; Ray, Biswajit; Maiti, Pralay; Misra, Nira

2017-09-20

Bone cement has found extensive usage in joint arthroplasty over the last 50 years; still, the development of bone cement with essential properties such as high fatigue resistance, lower exothermic temperature, and bioactivity has been an unsolved problem. In our present work, we have addressed all of the mentioned shortcomings of bone cement by reinforcing it with graphene (GR), graphene oxide (GO), and surface-modified amino graphene (AG) fillers. These nanocomposites have shown hypsochromic shifts, suggesting strong interactions between the filler material and the polymer matrix. AG-based nanohybrids have shown greater osteointegration and lower cytotoxicity compared to other nanohybrids as well as pristine bone cement. They have also reduced oxidative stress on cells, resulting in calcification within 20 days of the implantation of nanohybrids into the rabbits. They have significantly reduced the exothermic curing temperature to body temperature and increased the setting time to facilitate practitioners, suggesting that reaction temperature and settling time can be dynamically controlled by varying the concentration of the filler. Thermal stability and enhanced mechanical properties have been achieved in nanohybrids vis-à-vis pure bone cement. Thus, this newly developed nanocomposite can create natural bonding with bone tissues for improved bioactivity, longer sustainability, and better strength in the prosthesis.

Green process for green materials: viable low-temperature lipase-catalysed synthesis of renewable telechelics in supercritical CO2.

PubMed

Curia, S; Barclay, A F; Torron, S; Johansson, M; Howdle, S M

2015-12-28

We present a novel near-ambient-temperature approach to telechelic renewable polyesters by exploiting the unique properties of supercritical CO(2) (scCO(2)). Bio-based commercially available monomers have been polymerized and functional telechelic materials with targeted molecular weight prepared by end-capping the chains with molecules containing reactive moieties in a one-pot reaction. The use of scCO(2) as a reaction medium facilitates the effective use of Candida antarctica Lipase B (CaLB) as a catalyst at a temperature as low as 35°C, hence avoiding side reactions, maintaining the end-capper functionality and preserving the enzyme activity. The functionalized polymer products have been characterized by (1)H nuclear magnetic resonance spectroscopy, matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry, gel permeation chromatography and differential scanning calorimetry in order to carefully assess their structural and thermal properties. We demonstrate that telechelic materials can be produced enzymatically at mild temperatures, in a solvent-free system and using renewably sourced monomers without pre-modification, by exploiting the unique properties of scCO(2). The macromolecules we prepare are ideal green precursors that can be further reacted to prepare useful bio-derived films and coatings. © 2015 The Author(s).

An Approach to Processable Polyimides

NASA Technical Reports Server (NTRS)

Gariepy, Christopher A.; Eby, R. K.; Meador, Michael A.

1999-01-01

The use of polymer matrix composites (PMC's) in aircraft engines can lead to substantial weight savings over metals. This weight reduction correlates into better fuel economy, increased speed, and increased passenger load. Typically, high performance PMC's possess high thermal-oxidative stabilities (TOS) and high glass transition temperatures (Tg's) to withstand temperatures up to 316 C (600 F). One of the leading high temperature resins system available today is PMR-15 (Polymerization of Monomeric Reactants, MW=1500). This thermosetting polyimide utilizes addition curing through polymer endcaps which enables hand lay-up processing of carbon fiber composite parts with low void contents. However, the large amount of hand labor raises manufacturing costs and prohibits the use of PMR-15 in many aerospace applications. Resin Transfer Molding (RTM) provides an economical alternative, but it requires a melt Viscosity of less than 10(exp 3) centipoise (cP). This is much lower than the minimum melt viscosity of PMR-15 (about 10(exp 6) cP). To improve the processability of polyimides, the polymer backbone can be modified by incorporating flexible linkages, such as branching. bulky pendant groups, kinked structures, and twisted or non-coplanar moietes . The focus of this paper will be the introduction of non-coplanar biaryls into the PMR polyimide backbone to increase processability while maintaining high temperature performance.

Preparation and application of conducting polymer/Ag/clay composite nanoparticles formed by in situ UV-induced dispersion polymerization

PubMed Central

Zang, Limin; Qiu, Jianhui; Yang, Chao; Sakai, Eiichi

2016-01-01

In this work, composite nanoparticles containing polypyrrole, silver and attapulgite (PPy/Ag/ATP) were prepared via UV-induced dispersion polymerization of pyrrole using ATP clay as a templet and silver nitrate as photoinitiator. The effects of ATP concentration on morphology, structure and electrical conductivity were studied. The obtained composite nanoparticles with an interesting beads-on-a-string morphology can be obtained in a short time (10 min), which indicates the preparation method is facile and feasible. To explore the potential applications of the prepared PPy/Ag/ATP composite nanoparticles, they were served as multifunctional filler and blended with poly(butylene succinate) (PBS) matrix to prepare biodegradable composite material. The distribution of fillers in polymer matrix and the interfacial interaction between fillers and PBS were confirmed by scanning electron microscope, elemental mapping and dynamic mechanical analysis. The well dispersed fillers in PBS matrix impart outstanding antibacterial property to the biodegradable composite material as well as enhanced storage modulus due to Ag nanoparticles and ATP clay. The biodegradable composite material also possesses modest surface resistivity (106 ~ 109 Ω/◻). PMID:26839126

Hybrid self-healing matrix using core-shell nanofibers and capsuleless microdroplets.

PubMed

Lee, Min Wook; An, Seongpil; Lee, Changmin; Liou, Minho; Yarin, Alexander L; Yoon, Sam S

2014-07-09

In this work, we developed novel self-healing anticorrosive hierarchical coatings that consist of several components. Namely, as a skeleton we prepared a core-shell nanofiber mat electrospun from emulsions of cure material (dimethyl methylhydrogen siloxane) in a poly(acrylonitrile) (PAN) solution in dimethylformamide. In these nanofibers, cure is in the core, while PAN is in the shell. The skeleton deposited on a protected surface is encased in an epoxy-based matrix, which contains emulsified liquid droplets of dimethylvinyl-terminated dimethylsiloxane resin monomer. When such hierarchical coatings are damaged, cure is released from the nanofiber cores and the resin monomer, released from the damaged matrix, is polymerized in the presence of cure. This polymerization and solidification process takes about 1-2 days and eventually heals the damaged material when solid poly(dimethylsiloxane) resin is formed. The self-healing effect was demonstrated using an electrochemical analogue of the scanning vibrating electrode technique. Damaged samples were left for 2 days. After that, the electric current through a damaged coating was found to be negligibly small for the samples with self-healing properties. On the other hand, for the samples without self-healing properties, the electric current was significant.

Thermal and mechanical properties of palm oil-based polyurethane acrylate/clay nanocomposites prepared by in-situ intercalative method and electron beam radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salih, A. M.; Ahmad, Mansor Bin; Ibrahim, Nor Azowa

2014-02-12

Palm oil based-polyurethane acrylate (POBUA)/clay nanocomposites were prepared via in-situ intercalative polymerization using epoxidized palm oil acrylate (EPOLA) and 4,4' methylene diphenyl diisocyante (MDI). Organically modified Montmorillonite (ODA-MMT) was incorporated in EPOLA (1, 3 and 5%wt), and then subjected to polycondensation reaction with MDI. Nanocomposites solid films were obtained successfully by electron beam radiation induced free radical polymerization (curing). FTIR results reveal that the prepolymer was obtained successfully, with nanoclay dispersed in the matrix. The intercalation of the clay in the polymer matrix was investigated by XRD and the interlayer spacing of clay was found to be increased up tomore » 37 Å, while the structure morphology of the nanocomposites was investigated by TEM and SEM. The nanocomposites were found to be a mixture of exfoliated and intercalated morphologies. The thermal stability of the nanocomposites was significantly increased by incorporation of nanoclay into the polymer matrix. DSC results reveal that the Tg was shifted to higher values, gradually with increasing the amount of filler in the nanocomposites. Tensile strength and Young's modulus of the nanocomposites showed remarkable improvement compared to the neat POBUA.« less

Characterization of extracellular polymeric substances of Bacillus amyloliquefaciens SQR9 induced by root exudates of cucumber.

PubMed

Kimani, Veronicah Njeri; Chen, Lin; Liu, Yunpeng; Raza, Waseem; Zhang, Nan; Mungai, Lewis Kamau; Shen, Qirong; Zhang, Ruifu

2016-11-01

Bacillus amyloliquefaciens SQR9 is a plant growth-promoting rhizobacterium (PGPRs) that forms biofilm on the roots of plants and protects them from a variety of pathogens. In this study, we reported the effect of root exudates produced by cucumber (Cucumis sativus L.) at different developmental stages on the biochemical composition of the biofilm matrix of SQR9. The results showed that the amino acids present in the root exudates of cucumber were responsible for triggering biofilm formation of SQR9. In addition, when root exudates harvested at different growth phases of cucumber were used as carbon sources for biofilm formation, the resulting biofilm matrixes differed both quantitatively and qualitatively. The biofilm matrix was mostly composed of amino groups observed by confocal laser scanning microscope (CLSM) hence the proteins formed the major component of the resulting extracellular polymeric substances (EPS). The potential use of amino acid-based dietary supplements to control biofilm formation in the plants may be a viable option to improve agricultural productivity by recruiting beneficial association with PGPRs in the manufacture of bio fertilizers or bio controls. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and application of conducting polymer/Ag/clay composite nanoparticles formed by in situ UV-induced dispersion polymerization.

PubMed

Zang, Limin; Qiu, Jianhui; Yang, Chao; Sakai, Eiichi

2016-02-03

In this work, composite nanoparticles containing polypyrrole, silver and attapulgite (PPy/Ag/ATP) were prepared via UV-induced dispersion polymerization of pyrrole using ATP clay as a templet and silver nitrate as photoinitiator. The effects of ATP concentration on morphology, structure and electrical conductivity were studied. The obtained composite nanoparticles with an interesting beads-on-a-string morphology can be obtained in a short time (10 min), which indicates the preparation method is facile and feasible. To explore the potential applications of the prepared PPy/Ag/ATP composite nanoparticles, they were served as multifunctional filler and blended with poly(butylene succinate) (PBS) matrix to prepare biodegradable composite material. The distribution of fillers in polymer matrix and the interfacial interaction between fillers and PBS were confirmed by scanning electron microscope, elemental mapping and dynamic mechanical analysis. The well dispersed fillers in PBS matrix impart outstanding antibacterial property to the biodegradable composite material as well as enhanced storage modulus due to Ag nanoparticles and ATP clay. The biodegradable composite material also possesses modest surface resistivity (10(6)~ 10(9) Ω/◻).

BslA(YuaB) forms a hydrophobic layer on the surface of Bacillus subtilis biofilms.

PubMed

Kobayashi, Kazuo; Iwano, Megumi

2012-07-01

Biofilms are surface-associated bacterial aggregates, in which bacteria are enveloped by polymeric substances known as the biofilm matrix. Bacillus subtilis biofilms display persistent resistance to liquid wetting and gas penetration, which probably explains the broad-spectrum resistance of the bacteria in these biofilms to antimicrobial agents. In this study, BslA (formerly YuaB) was identified as a major contributor to the surface repellency of B. subtilis biofilms. Disruption of bslA resulted in the loss of surface repellency and altered the biofilm surface microstructure. BslA localized to the biofilm matrix in an exopolysaccharide-dependent manner. Purified BslA exhibited amphiphilic properties and formed polymers in response to increases in the area of the air-water interface in vitro. Genetic and biochemical analyses showed that the self-polymerization activity of BslA was essential for its ability to localize to the biofilm matrix. Confocal laser scanning microscopy showed that BslA formed a layer on the biofilm surface. Taken together, we propose that BslA, standing for biofilm-surface layer protein, is responsible for the hydrophobic layer on the surface of biofilms. © 2012 Blackwell Publishing Ltd.

Preparation and characterization of poly(acrylic acid)-hydroxyethyl cellulose graft copolymer.

PubMed

Abdel-Halim, E S

2012-10-01

Poly(acrylic acid) hydroxyethyl cellulose [poly(AA)-HEC] graft copolymer was prepared by polymerizing acrylic acid (AA) with hydroxyethyl cellulose (HEC) using potassium bromate/thiourea dioxide (KBrO(3)/TUD) as redox initiation system. The polymerization reaction was carried out under a variety of conditions including concentrations of AA, KBrO(3) and TUD, material to liquor ratio and polymerization temperature. The polymerization reaction was monitored by withdrawing samples from the reaction medium and measuring the total conversion. The rheological properties of the poly(AA)-HEC graft copolymer were investigated. The total conversion and rheological properties of the graft copolymer depended on the ratio of KBrO(3) to TUD and on acrylic acid concentration as well as temperature and material to liquor ratio. Optimum conditions of the graft copolymer preparation were 30 mmol KBrO(3) and 30 mmol TUD/100g HEC, 100% AA (based on weight of HEC), duration 2h at temperature 50 °C using a material to liquor ratio of 1:10. Copyright © 2012. Published by Elsevier Ltd.

MAPLE deposited polymeric blends coatings for controlled drug delivery

NASA Astrophysics Data System (ADS)

Paun, Irina Alexandra; Ion, Valentin; Moldovan, Antoniu; Dinescu, Maria

2012-07-01

We report on the use of Matrix Assisted Pulsed Laser Evaporation (MAPLE) for producing coatings of polymer blends for controlled drug delivery. The coatings consisting of blends of polyethylene glycol: poly(lactide-co-glycolide) (PEG: PLGA blends) are compared with those consisting of individual polymers (PEG, PLGA) in terms of chemical composition, morphology, hydrophilicity and optical constants. The release kinetics of an anti-inflammatory drug (indomethacin) through the polymeric coatings is monitored and possible mechanisms of the drug release are discussed. Furthermore, the compatibility of the polymeric coatings with blood constituents is investigated. Finally, the perspectives for employing MAPLE for producing coatings of polymer blends to be used in implants that deliver drugs in a controlled manner, along with the routes to be followed for elucidating the mechanism of drug release, are revealed.

Dual functions of imidazole-based polymeric ionic liquid (PIL) on the anticorrosive performance of graphene-based waterborne epoxy coatings

NASA Astrophysics Data System (ADS)

Liu, Chengbao; Du, Peng; Nan, Feng; Zhao, Haichao; Wang, Liping

2018-06-01

Dispersion of graphene nanosheets in a water and polymer matrix has been rarely achieved due to graphene’s hydrophobicity, which thus impedes its potential anticorrosive application. In this study, stable graphene aqueous dispersion was obtained by using imidazole-based polymeric ionic liquid (PIL) as the dispersant with ultrasonic vibration. Stacked graphene sheets were exfoliated to a few layers via cation-π interaction between PIL and graphene nanosheets. Electrochemical impedance measurements were taken to investigate the anticorrosion performance of epoxy coatings with or without polymeric ionic liquid–graphene (PIL–G) hybrids. Results indicated that the PIL–G hybrid significantly enhanced the long-term protective performance of epoxy coatings, which was attributed to the synergistic effects of the corrosion-inhibitive PIL and impermeable graphene nanosheets.

Influence of residual composition on the structure and properties of extracellular matrix derived hydrogels.

PubMed

Claudio-Rizo, Jesús A; Rangel-Argote, Magdalena; Castellano, Laura E; Delgado, Jorge; Mata-Mata, José L; Mendoza-Novelo, Birzabith

2017-10-01

In this work, hydrolysates of extracellular matrix (hECM) were obtained from rat tail tendon (TR), bovine Achilles tendon (TAB), porcine small intestinal submucosa (SIS) and bovine pericardium (PB), and they were polymerized to generate ECM hydrogels. The composition of hECM was evaluated by quantifying the content of sulphated glycosaminoglycans (sGAG), fibronectin and laminin. The polymerization process, structure, physicochemical properties, in vitro degradation and biocompatibility were studied and related to their composition. The results indicated that the hECM derived from SIS and PB were significantly richer in sGAG, fibronectin and laminin, than those derived from TAB and TR. These differences in hECM composition influenced the polymerization and the structural characteristics of the fibrillar gel network. Consequently, the swelling, mechanics and degradation of the hydrogels showed a direct relationship with the remaining composition. Moreover, the cytocompatibility and the secretion of transforming growth factor beta-1 (TGF-β1) by macrophages were enhanced in hydrogels with the highest residual content of ECM biomolecules. The results of this work evidenced the role of the ECM molecules remaining after both decellularization and hydrolysis steps to produce tissue derived hydrogels with structure and properties tailored to enhance their performance in tissue engineering and regenerative medicine applications. Copyright © 2017 Elsevier B.V. All rights reserved.

The Microwave Assisted Composite Manufacturing and Repair (MACMAR) Project

NASA Technical Reports Server (NTRS)

Falker, John; Terrier, Douglas; Clayton, Ronald G.; Worthy, Erica; Sosa, Edward

2015-01-01

The inherent microwave property of carbon nanotubes (CNTs) generates the thermal energy required to induce reversible polymerization of the matrix in these self-healing composites. Microwaves will be used to demonstrate advanced composite manufacturing and repair using self-healing composites.

Controlled Bioactive Molecules Delivery Strategies for Tendon and Ligament Tissue Engineering using Polymeric Nanofibers.

PubMed

Hiong Teh, Thomas Kok; Hong Goh, James Cho; Toh, Siew Lok

2015-01-01

The interest in polymeric nanofibers has escalated over the past decade given its promise as tissue engineering scaffolds that can mimic the nanoscale structure of the native extracellular matrix. With functionalization of the polymeric nanofibers using bioactive molecules, localized signaling moieties can be established for the attached cells, to stimulate desired biological effects and direct cellular or tissue response. The inherently high surface area per unit mass of polymeric nanofibers can enhance cell adhesion, bioactive molecules loading and release efficiencies, and mass transfer properties. In this review article, the application of polymeric nanofibers for controlled bioactive molecules delivery will be discussed, with a focus on tendon and ligament tissue engineering. Various polymeric materials of different mechanical and degradation properties will be presented along with the nanofiber fabrication techniques explored. The bioactive molecules of interest for tendon and ligament tissue engineering, including growth factors and small molecules, will also be reviewed and compared in terms of their nanofiber incorporation strategies and release profiles. This article will also highlight and compare various innovative strategies to control the release of bioactive molecules spatiotemporally and explore an emerging tissue engineering strategy involving controlled multiple bioactive molecules sequential release. Finally, the review article concludes with challenges and future trends in the innovation and development of bioactive molecules delivery using polymeric nanofibers for tendon and ligament tissue engineering.

Nanostructured hybrid hydrogels prepared by a combination of atom transfer radical polymerization and free radical polymerization

PubMed Central

Bencherif, Sidi A.; Siegwart, Daniel J.; Srinivasan, Abiraman; Horkay, Ferenc; Hollinger, Jeffrey O.; Washburn, Newell R.; Matyjaszewski, Krzysztof

2012-01-01

A new method to prepare nanostructured hybrid hydrogels by incorporating well-defined poly(oligo (ethylene oxide) monomethyl ether methacrylate) (POEO300MA) nanogels of sizes 110–120 nm into a larger three-dimensional (3D) matrix was developed for drug delivery scaffolds for tissue engineering applications. Rhodamine B isothiocyanate-labeled dextran (RITC-Dx) or fluorescein isothiocyanate-labeled dextran (FITC-Dx)-loaded POEO300MA nanogels with pendant hydroxyl groups were prepared by activators generated electron transfer atom transfer radical polymerization (AGET ATRP) in cyclohexane inverse miniemulsion. Hydroxyl-containing nanogels were functionalized with methacrylated groups to generate photoreactive nanospheres. 1H NMR spectroscopy confirmed that polymerizable nanogels were successfully incorporated covalently into 3D hyaluronic acid-glycidyl methacrylate (HAGM) hydrogels after free radical photo-polymerization (FRP). The introduction of disulfide moieties into the polymerizable groups resulted in a controlled release of nanogels from cross-linked HAGM hydrogels under a reducing environment. The effect of gel hybridization on the macroscopic properties (swelling and mechanics) was studied. It is shown that swelling and nanogel content are independent of scaffold mechanics. In-vitro assays showed the nanostructured hybrid hydrogels were cytocompatible and the GRGDS (Gly–Arg–Gly–Asp–Ser) contained in the nanogel structure promoted cell–substrate interactions within 4 days of incubation. These nanostructured hydrogels have potential as an artificial extracellular matrix (ECM) impermeable to low molecular weight biomolecules and with controlled pharmaceutical release capability. Moreover, the nanogels can control drug or biomolecule delivery, while hyaluronic acid based-hydrogels can act as a macroscopic scaffold for tissue regeneration and regulator for nanogel release. PMID:19592087

[Evaluation of the Peusner's coefficients matrix for polymeric membrane and ternary non-electrolyte solutions].

PubMed

Jasik-Slęzak, Jolanta; Slęzak-Prochazka, Izabella; Slęzak, Andrzej

2014-01-01

A system of network forms of Kedem-Katchalsky (K-K) equations for ternary non-electrolyte solutions is made of eight matrix equations containing Peusner's coefficients R(ij), L(ij), H(ij), W(ij), K(ij), N(ij), S(ij) or P(ij) (i, j ∈ {1, 2, 3}). The equations are the result of symmetric or hybrid transformation of the classic form of K-K equations by the use of methods of Peusner's network thermodynamics (PNT). Calculating concentration dependences of the determinant of Peusner's coefficients matrixes R(ij), L(ij), H(ij), W(ij), S(ij), N(ij), K(ij) and P(ij) (i, j ∈ {1, 2, 3}). The material used in the experiment was a hemodialysis Nephrophan membrane with specified transport properties (L(p), σ, Ω) in aqueous glucose and ethanol solution. The method involved equations for determinants of the matrixes coefficients R(ij), L(ij), H(ij), W(ij), S(ij), N(ij), K(ij) or P(ij) (i, j ∈ {1, 2, 3}). The objective of calculations were dependences of determinants of Peusner's coeffcients matrixes R(ij), L(ij), H(ij), W(ij), S(ij), N(ij), K(ij) or P(ij) (i, j ∈ {1, 2, 3}) within the conditions of solution homogeneity upon an average concentration of one component of solution in the membrane (C1) with a determined value of the second component (C2). The method of calculating the determinants of Peusner's coeffcients matrixes R(ij), L(ij), H(ij), W(ij), S(ij), N(ij), K(ij) or P(ij) (i, j ∈ {1, 2, 3}) is a new tool that may be applicable in studies on membrane transport. Calculations showed that the coefficients are sensitive to concentration and composition of solutions separated by a polymeric membrane.

Localized in situ polymerization on graphene surfaces for stabilized graphene dispersions.

PubMed

Das, Sriya; Wajid, Ahmed S; Shelburne, John L; Liao, Yen-Chih; Green, Micah J

2011-06-01

We demonstrate a novel in situ polymerization technique to develop localized polymer coatings on the surface of dispersed pristine graphene sheets. Graphene sheets show great promise as strong, conductive fillers in polymer nanocomposites; however, difficulties in dispersion quality and interfacial strength between filler and matrix have been a persistent problem for graphene-based nanocomposites, particularly for pristine graphene. With this in mind, a physisorbed polymer layer is used to stabilize graphene sheets in solution. To create this protective layer, we formed an organic microenvironment around dispersed graphene sheets in surfactant solutions, and created a nylon 6, 10 or nylon 6, 6 coating via interfacial polymerization. Technique lies at the intersection of emulsion and admicellar polymerization; a similar technique was originally developed to protect luminescent properties of carbon nanotubes in solution. These coated graphene dispersions are aggregation-resistant and may be reversibly redispersed in water even after freeze-drying. The coated graphene holds promise for a number of applications, including multifunctional graphene-polymer nanocomposites. © 2011 American Chemical Society

Near-Edge X-ray Absorption Fine Structure Studies of Electrospun Poly(dimethylsiloxane)/Poly (methyl methacrylate)/Multiwall Carbon Nanotube Composites

PubMed Central

Winter, A. Douglas; Larios, Eduardo; Alamgir, Faisal M.; Jaye, Cherno; Fischer, Daniel; Campo, Eva M.

2014-01-01

This work describes the near conduction band edge structure of electrospun mats of MWCNT-PDMS-PMMA by near edge X-Ray absorption fine structure (NEXAFS) spectroscopy. Effects of adding nanofillers of different sizes were addressed. Despite observed morphological variations and inhomogeneous carbon nanotube distribution, spun mats appeared homogeneous under NEXAFS analysis. Spectra revealed differences in emissions from glancing and normal spectra; which may evidence phase separation within the bulk of the micron-size fibers. Further, dichroic ratios show polymer chains did not align, even in the presence of nanofillers. Addition of nanofillers affected emissions in the C-H, C=O and C-C regimes, suggesting their involvement in interfacial matrix-carbon nanotube bonding. Spectral differences at glancing angles between pristine and composite mats suggest that geometric conformational configurations are taking place between polymeric chains and carbon nanotubes. These differences appear to be carbon nanotube-dimension dependent, and are promoted upon room temperature mixing and shear flow during electrospinning. CH-π bonding between polymer chains and graphitic walls, as well as H-bonds between impurities in the as-grown CNTs and polymer pendant groups are proposed bonding mechanisms promoting matrix conformation. PMID:24308286

Electrical bistability in conductive hybrid composites of doped polyaniline nanofibers-gold nanoparticles capped with dodecane thiol.

PubMed

Borriello, A; Agoretti, P; Cassinese, A; D'Angelo, P; Mohanraj, G T; Sanguigno, L

2009-11-01

A novel electrical bistable hybrid nanocomposite based on doped Polyaniline nanofibers with 1-Dodecanethiol-protected Gold nanoparticle (PAni.AuDT), 3-4 nm in size, as the conductive component and polystyrene as polymer matrix was prepared. The structural morphology of the composite and the dispersion of nanoparticles inside it were evaluated using Transmission Electron Microscopy (TEM). The thermal stability and the ratio Polyaniline/Gold nanoparticles in the composite were determined by using thermogravimetric analysis. The electrical bistability of the PAni.AuDT-PS composite, the influence of the dispersion of the PAni.AuDT conductive network and the basic operation mechanism, have been assessed by measuring the electrical response of planar device architectures, also as a function of the environmental temperature (in the range 200 K < T < 360 K). The basic operation mechanism of the hybrid compound has been then correlated to the combined action of the thermally-induced scattering of charge carriers and the thermal contraction of the hosting polymeric matrix. Moreover, the right compromise between these two effects in terms of the most efficient bistability has been studied, founding the concentration of the conductive component which optimizes the device on-off ratio (I(on)/ I(off)).

Aerospace materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dornheim, M.A.

1991-04-01

A comprehensive evaluation is made of the development trends in high performance advanced aerospace structural materials applications. It is noted that the anticipated predominance of thermoplastic composite-matrix polymers in the F-22/F-23 ATF propotypes has not materialized, due both to their high materials and processing costs and the emergence of a more tractable high operating temperature thermoset, BMI, whose toughness characteristics are of the order of those associated with thermoplastics. No more than 15 percent of F-22 weight is thermoplastics; the F-23 use of such resins is nill. Throughout the advanced nonmetallics industry, reduced DOD procurements have come to represent slowmore » growth and the prospect of consolidation. Also, such lightweight Al-based metallics as the Al-Li alloys have posed a major market-share challenge to polymeric composites, as in the case of the C-17 airlifter's 6,269 lbs of such Al-Li alloys as 2090, largely in cargo floor and ramp bulkhead structures. The EFA fighter makes frequent use of SPF-DB Ti alloys in combat damage-critical components. Metal-matrix composites employing titanium aluminide matrices will be extensively used in the X-30 hypersonic aircraft program.« less

Synthesis biolubricant from rubber seed oil

NASA Astrophysics Data System (ADS)

Hung, Nguyen Tran Dong; Tuyen, Dang Thi Hong; Viet, Tran Tan

2017-09-01

The objective was biolubricant preparation from rubber seed oil (RSO) using polymerization reactor with/without catalyst in batch reactor. Before become reactant in polymerization reaction, a non-edible rubber seed oil was converted into methyl ester by esterification/tranesterification reaction with methanol and acid/base catalyst. The polymerization reaction parameters investigated were reaction time, temperature and weight ratio (catalyst with feed), and their effect on the bio lubricant formation. The result show significant conversion of methyl ester to bio lubricant in the temperature reaction of 160°C, reaction time of 2h min and ratio of super acid catalyst (tetrafluoroboric acid-sHBF4) of 3 %w/w. The resulting products were confirmed by GC-MS, FTIR spectroscopy and also analyzed for the viscosity. The best viscosity value of RSOFAME polymer was 110.6 cSt when the condition polymerization reaction were 160 °C, reaction time 3h, 6 wt% mass ratio of oil:catalyst.

Influence of the volumes of bis-acryl and poly(methyl methacrylate) resins on their exothermic behavior during polymerization.

PubMed

Ha, Jung-Yun; Kim, Sung-Hun; Kim, Kyo-Han; Kwon, Tae-Yub

2011-01-01

This study aimed to evaluate the influence of the volumes of a bis-acryl resin (Luxatemp) and a poly(methyl methacrylate) resin (Jet) on their exothermic behaviors during polymerization based on vinyl group conversion. The number of vinyl groups reacted and exotherm were determined based on weight percent of methacrylate groups using FTIR spectroscopy. Temperature changes during polymerization at 23°C were recorded for 20 minutes using a multiple cavity mold overlying a thermocouple. The number of vinyl groups reacted and exotherm of Luxatemp were consistently lower than those of Jet at each resin volume. Mean peak temperature rises of Luxatemp and Jet were in the range of 2.0-6.6°C and 4.2-11.6°C respectively, with Luxatemp and Jet taking 2 and 10 minutes respectively to reach their peak temperatures. As their resin volumes increased, their peak temperatures and total peak areas were also observed to increase significantly (p<0.01).

Investigation of the deformation mechanisms of core-shell rubber-modified epoxy at cryogenic temperatures

NASA Astrophysics Data System (ADS)

Brown, Hayley Rebecca

The industrial demand for high strength-to-weight ratio materials is increasing due to the need for high performance components. Epoxy polymers, although often used in fiber-reinforced polymeric composites, have an inherent low toughness that further decreases with decreasing temperatures. Second-phase additives have been effective in increasing the toughness of epoxies at room temperature; however, the mechanisms at low temperatures are still not understood. In this study, the deformation mechanisms of a DGEBA epoxy modified with MX960 core-shell rubber (CSR) particles were investigated under quasi-static tensile and impact loads at room temperature (RT) and liquid nitrogen (LN 2) temperature. Overall, the CSR had little effect on the tensile properties at RT and LN2 temperature. The impact strength decreased from neat to 3 wt% but increased from neat to 5 wt% at RT and LN2 temperature, with a higher impact strength at RT at all CSR loadings. The CSR particles debonded in front of the crack tip, inducing voids into the matrix. It was found that an increase in shear deformation and void growth likely accounted for the higher impact strength at 5 wt% CSR loading at RT while the thermal stress fields due to the coefficient of thermal expansion mismatch between rubber and epoxy and an increase in secondary cracking is likely responsible for the higher impact strength at 5 wt% tested at LN2 temperature. While a large toughening effect was not seen in this study, the mechanisms analyzed herein will likely be of use for further material investigations at cryogenic temperatures.

Functional organization of mitotic microtubules. Physical chemistry of the in vivo equilibrium system.

PubMed Central

Inoué, S; Fuseler, J; Salmon, E D; Ellis, G W

1975-01-01

Equilibrium between mitotic microtubules and tubulin is analyzed, using birefringence of mitotic spindle to measure microtubule concentration in vivo. A newly designed temperature-controlled slide and miniature, thermostated hydrostatic pressure chamber permit rapid alteration of temperature and of pressure. Stress birefringence of the windows is minimized, and a system for rapid recording of compensation is incorporated, so that birefringence can be measured to 0.1 nm retardation every few seconds. Both temperature and pressure data yield thermodynamic values (delta H similar to 35 kcal/mol, delta S similar to 120 entropy units [eu], delta V similar to 400 ml/mol of subunit polymerized) consistent with the explanation that polymerization of tubulin is entropy driven and mediated by hydrophobic interactions. Kinetic data suggest pseudo-zero-order polymerization and depolymerization following rapid temperature shifts, and a pseudo-first-order depolymerization during anaphase at constant temperature. The equilibrium properties of the in vivo mitotic microtubules are compared with properties of isolated brain tubules. Images FIGURE 1 FIGURE 2 FIGURE 5 FIGURE 12 FIGURE 13 FIGURE 14 FIGURE 19 PMID:1139037

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes

NASA Astrophysics Data System (ADS)

Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

2015-11-01

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

Metallocene Catalytic Insertion Polymerization of 1-Silene to Polycarbosilanes.

PubMed

Tian, Yuelong; Ge, Min; Zhang, Weigang; Lv, Xiaoxu; Yu, Shouquan

2015-11-06

Metallocene of zirconium were used as a catalyst for an insertion polymerization of 1-methylsilene directly into pre-ceramic precursor polyzirconocenecarbosilane (PZCS) during dechlorination of dichlorodimethylesilane by sodium, which exhibits high catalytic effectiveness with the maximum conversion ratio of polycarbosilane up to 91%. The average molecular weights of polymers synthesized are less than 1400, all with very narrow polymolecularities. The mechanism of catalytic polymerization was assumed to be similar to a coordination insertion polymerization of 1-olefins by metallocenes. The obtained PZCS show high ceramic yields with formation of composite ceramics of ZrC-SiC, which are novel polymeric precursors of ultra-high temperature ceramic (UHTC) fiber and composite.

The Effect of Curing Temperature on the Fracture Toughness of Fiberglass Epoxy Composites

NASA Astrophysics Data System (ADS)

Ryan, Thomas J.

The curing reaction in a thermoset polymer matrix composite is often accelerated by the addition of heat in an oven or autoclave. The heat added increases the rate of the polymerization reaction and cross-linking in the material. The cure cycle used (temperature, pressure and time) can therefore alter the final material properties. This research focuses on how the curing temperature (250, 275, 300 °F) affects the yield strength and the mode I interlaminar fracture toughness, GI, of a unidirectional S-2 glass epoxy composite. The test method that was used for the tension test was ASTM D3039 and the test method for the mode I interlaminar fracture toughness, the double cantilever beam (DCB) test, was ASTM D5528. The DCB specimens were fabricated with a non-adhesive insert at the midplane of the composite that serves as the initiatior of the delamination. Opening forces were then applied to the specimen, causing the crack propagation. The results show that increasing the cure temperature by 50 °F increased the tensile strength by 10% (86.54 - 94.73 ksi) and decreased the fracture toughness 20% (506.23 - 381.31 J/m 2). Thus, the curing temperature can cause a trade-off between these two properties, which means that the curing cycle will need to be altered based on the intended use and the required material properties.

Water as a matrix for life

NASA Technical Reports Server (NTRS)

Pohorille, Andrew

2005-01-01

Life is based on non-covalent interactions. They might be either specific (enzyme-substrate interactions, selective ion transport) or nonspecific (lipid-lipid and lipid-protein interactions needed for membrane integrity, fusion and division). Their strength needs to be properly tuned, and this is mediated by the solvent. If interactions are too weak, there might be undesired response to natural fluctuations of physical and chemical parameters. If they are too strong it could impede kinetics and energetics of cellular processes. Thus, the solvent must allow for balancing these interactions. Physical and chemical properties of solvent provide strong constraints for life. Water exhibits a remarkable trait that it promotes both solvophobic and solvophilic interactions. Solvophobic interactions; related to high dielectric constant of the solvent) are necessary for self-organization of matter whereas solvophilic interactions are needed to ensure solubility of polar species. Water offers a large temperature domain of stable liquid and the characteristics hydrophobic effects are a consequence of the temperature in sensitivity of essential properties of its liquid state. Water, however, is not the only liquid with these favorable properties. I will compare in detail properties of water and other pure liquids or their mixtures that have a high dielectric constant and simultaneously support self-organization. I will also discuss properties of water that are unfavorable to life (e.g. its chemical activity against polymerization reactions) and close with summarizing what are alternatives to water as a matrix of life in space.

Luminescence properties of femtosecond-laser-activated silver oxide nanoparticles embedded in a biopolymer matrix

NASA Astrophysics Data System (ADS)

Gleitsmann, T.; Bernhardt, T. M.; Wöste, L.

2006-01-01

Strong visible luminescence is observed from silver clusters generated by femtosecond-laser-induced reduction of silver oxide nanoparticles embedded in a polymeric gelatin matrix. Light emission from the femtosecond-laser-activated matrix areas considerably exceeds the luminescence intensity of similarly activated bare silver oxide nanoparticle films. Optical spectroscopy of the activated polymer films supports the assignment of the emissive properties to the formation of small silver clusters under focused femtosecond-laser irradiation. The size of the photogenerated clusters is found to sensitively depend on the laser exposure time, eventually leading to the formation of areas of metallic silver in the biopolymer matrix. In this case, luminescence can still be observed in the periphery of the metallic silver structures, emphasizing the importance of the organic matrix for the stabilization of the luminescent nanocluster structures at the metal matrix interface.

Preparation and characterization of polyaniline-cadmium sulfide nanocomposite for gas sensor application

NASA Astrophysics Data System (ADS)

Al-Jawad, Selma M. H.; Rafic, Sewench N.; Muhsen, Mustafa M.

2017-09-01

Polyaniline (PANI) was prepared by chemical oxidative polymerization of aniline monomers as emeraldine salt form. By the same method, polyaniline-cadmium sulfide nanocomposites were synthesized in the presence of different percentages (10-50 wt.%) of cadmium sulfide (CdS) which was prepared by using sol-gel method. The optical band gap was decrease with increasing of CdS concentration, that is obtained from UV-VIS measurements. From SEM and AFM, there is uniform distribution for cadmium sulfide nanoparticles in the PANI matrix. The electrical measurements of nanocomposites exhibit the effect of crystallite size and the high resistivity of CdS on the resistivity of nanocomposites. Emeraldine salt PANI, CdS and PANI-CdS nanocomposites were investigated as gas sensors. From this investigation, the sensitivity of PANI-CdS for NO2 gas increase with the increasing of operation temperature and the optimum sensitivity was obtained at 200∘C. The sensitivity of nanocomposites at best temperature (200∘C) was increased and faster response time with the increasing of CdS contents.

Self-healing coatings containing microcapsule

NASA Astrophysics Data System (ADS)

Zhao, Yang; Zhang, Wei; Liao, Le-ping; Wang, Si-jie; Li, Wu-jun

2012-01-01

Effectiveness of epoxy resin filled microcapsules was investigated for healing of cracks generated in coatings. Microcapsules were prepared by in situ polymerization of urea-formaldehyde resin to form shell over epoxy resin droplets. Characteristics of these capsules were studied by 3D measuring laser microscope, particle size analyzer, Fourier-transform infrared spectroscopy (FTIR) and differential scanning calorimeter (DSC) to investigate their surface morphology, size distribution, chemical structure and thermal stability, respectively. The results indicate that microcapsules containing epoxy resins can be synthesized successfully. The size is around 100 μm. The rough outer surface of microcapsule is composed of agglomerated urea-formaldehyde nanoparticles. The size and surface morphology of microcapsule can be controlled by selecting different processing parameters. The microcapsules basically exhibit good storage stability at room temperature, and they are chemically stable before the heating temperature is up to approximately 200 °C. The model system of self-healing coating consists of epoxy resin matrix, 10 wt% microencapsulated healing agent, 2 wt% catalyst solution. The self-healing function of this coating system is evaluated through self-healing testing of damaged and healed coated steel samples.

A Thermochromic Superhydrophobic Surface

PubMed Central

Cataldi, Pietro; Bayer, Ilker S.; Cingolani, Roberto; Marras, Sergio; Chellali, Ryad; Athanassiou, Athanassia

2016-01-01

Highly enhanced solid-state thermochromism is observed in regioregular poly(3-hexylthiophene), P3HT, when deposited on a superhydrophobic polymer-SiO2 nanocomposite coating. The conformal P3HT coating on the nanocomposite surface does not alter or reduce superhydrophicity while maintaining its reversible enhanced thermochromism. The polymeric matrix of the superhydrophobic surface is comprised of a blend of poly(vinylidene fluoride-co-hexafluoropropylene) copolymer and an acrylic adhesive. Based on detailed X-ray diffraction measurements, this long-lasting, repeatable and hysteresis-free thermochromic effect is attributed to the enhancement of the Bragg peak associated with the d-spacing of interchain directional packing (100) which remains unaltered during several heating-cooling cycles. We propose that the superhydrophobic surface confines π–π interchain stacking in P3HT with uniform d-spacing into its nanostructured texture resulting in better packing and reduction in face-on orientation. The rapid response of the system to sudden temperature changes is also demonstrated by water droplet impact and bounce back on heated surfaces. This effect can be exploited for embedded thin film temperature sensors for metal coatings. PMID:27301422

From oligomers to molecular giants of soybean oil in supercritical carbon dioxide medium: 1. Preparation of polymers with lower molecular weight from soybean oil.

PubMed

Liu, Zengshe; Sharma, Brajendra K; Erhan, Sevim Z

2007-01-01

Polymers with a low molecular weight derived from soybean oil have been prepared in a supercritical carbon dioxide medium by cationic polymerization. Boron trifluoride diethyl etherate was used as an initiator. Influences of polymerization temperature, amount of initiator, and carbon dioxide pressure on the molecular weight were investigated. It is shown that the higher polymerization temperature favors polymers with relatively higher molecular weights. Larger amounts of initiator also provide polymers with higher molecular weights. Higher pressure favors polymers with relatively higher molecular weights. The applications of these soy-based materials will be in the lubrication and hydraulic fluid areas.

In vivo non-invasive optical imaging of temperature-sensitive co-polymeric nanohydrogel

NASA Astrophysics Data System (ADS)

Chen, Haiyan; Zhang, Jian; Qian, Zhiyu; Liu, Fei; Chen, Xinyang; Hu, Yuzhu; Gu, Yueqing

2008-05-01

Assessment of hyperthermia in pathological tissue is a promising strategy for earlier diagnosis of malignant tumors. In this study, temperature-sensitive co-polymeric nanohydrogel poly(N-isopropylacrylamide-co-acrylic acid) (PNIPA-co-AA) was successfully synthesized by the precipitation polymerization method. The diameters of nanohydrogels were controlled to be less than 100 nm. Also the lower critical solution temperature (LCST, 40 °C) was manipulated above physiological temperature after integration of near-infrared (NIR) organic dye (heptamethine cyanine dye, HMCD) within its interior cores. NIR laser light (765 nm), together with sensitive charge coupled device (CCD) cameras, were designed to construct an NIR imaging system. The dynamic behaviors of PNIPA-co-AA-HMCD composites in denuded mice with or without local hyperthermia treatment were real-time monitored by an NIR imager. The results showed that the PNIPA-co-AA-HMCD composites accumulated in the leg treated with local heating and diffused much slower than that in the other leg without heating. The results demonstrated that the temperature-responsive PNIPA-co-AA-HMCD composites combining with an NIR imaging system could be an effective temperature mapping technique, which provides a promising prospect for earlier tumor diagnosis and thermally related therapeutic assessment.

Matrix-assisted laser desorption/ionization mass spectrometric analysis of poly(3,4-ethylenedioxythiophene) in solid-state dye-sensitized solar cells: comparison of in situ photoelectrochemical polymerization in aqueous micellar and organic media.

PubMed

Zhang, Jinbao; Ellis, Hanna; Yang, Lei; Johansson, Erik M J; Boschloo, Gerrit; Vlachopoulos, Nick; Hagfeldt, Anders; Bergquist, Jonas; Shevchenko, Denys

2015-04-07

Solid-state dye-sensitized solar cells (sDSCs) are devoid of such issues as electrolyte evaporation or leakage and electrode corrosion, which are typical for traditional liquid electrolyte-based DSCs. Poly(3,4-ethylenedioxythiophene) (PEDOT) is one of the most popular and efficient p-type conducting polymers that are used in sDSCs as a solid-state hole-transporting material. The most convenient way to deposit this insoluble polymer into the dye-sensitized mesoporous working electrode is in situ photoelectrochemical polymerization. Apparently, the structure and the physicochemical properties of the generated conducting polymer, which determine the photovoltaic performance of the corresponding solar cell, can be significantly affected by the preparation conditions. Therefore, a simple and fast analytical method that can reveal information on polymer chain length, possible chemical modifications, and impurities is strongly required for the rapid development of efficient solar energy-converting devices. In this contribution, we applied matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) for the analysis of PEDOT directly on sDSCs. It was found that the PEDOT generated in aqueous micellar medium possesses relatively shorter polymeric chains than the PEDOT deposited from an organic medium. Furthermore, the micellar electrolyte promotes a transformation of one of the thiophene terminal units to thiophenone. The introduction of a carbonyl group into the PEDOT molecule impedes the growth of the polymer chain and reduces the conductivity of the final polymer film. Both the simplicity of sample preparation (only application of the organic matrix onto the solar cell is needed) and the rapidity of analysis hold the promise of making MALDI MS an essential tool for the physicochemical characterization of conducting polymer-based sDSCs.

Silica Coating of Nonsilicate Nanoparticles for Resin-Based Composite Materials

PubMed Central

Kaizer, M.R.; Almeida, J.R.; Gonçalves, A.P.R.; Zhang, Y.; Cava, S.S.; Moraes, R.R.

2016-01-01

This study was designed to develop and characterize a silica-coating method for crystalline nonsilicate ceramic nanoparticles (Al2O3, TiO2, and ZrO2). The hypothesis was that the coated nonsilicate nanoparticles would stably reinforce a polymeric matrix due to effective silanation. Silica coating was applied via a sol-gel method, with tetraethyl orthosilicate as a silica precursor, followed by heat treatment. The chemical and microstructural characteristics of the nanopowders were evaluated before and after silica coating through x-ray diffraction, BET (Brunauer-Emmett-Teller), energy-dispersive x-ray spectroscopy, field emission scanning electron microscopy, and transmission electron microscopy analyses. Coated and noncoated nanoparticles were silanated before preparation of hybrid composites, which contained glass microparticles in addition to the nanoparticles. The composites were mechanically tested in 4-point bending mode after aging (10,000 thermal cycles). Results of all chemical and microstructural analyses confirmed the successful obtaining of silica-coated nanoparticles. Two distinct aspects were observed depending on the type of nanoparticle tested: 1) formation of a silica shell on the surface of the particles and 2) nanoparticle clusters embedded into a silica matrix. The aged hybrid composites formulated with the coated nanoparticles showed improved flexural strength (10% to 30% higher) and work of fracture (35% to 40% higher) as compared with composites formulated with noncoated nanoparticles. The tested hypothesis was confirmed: silanated silica-coated nonsilicate nanoparticles yielded stable reinforcement of dimethacrylate polymeric matrix due to effective silanation. The silica-coating method presented here is a versatile and promising novel strategy for the use of crystalline nonsilicate ceramics as a reinforcing phase of polymeric composite biomaterials. PMID:27470069

Natural and Synthetic Biohydrogels Design, Characterization, Network Structure Imaging and Modeling

NASA Astrophysics Data System (ADS)

Marmorat, Clement

Biocompatible hydrogels can be derived from materials that are naturally obtained, such as proteins or polysaccharides, or synthetic, such as poloxamers. In order to be classified as biocompatible, these water-swollen networks can not trigger a toxic response once introduced into a biological or physiological environment and, therefore, must be immunoneutral. Hyaluronic acid hydrogels can be great candidates for tissue engineering applications as long as the cross-linking chemistry and process does not affect the biocompatibility of the natural protein matrix. Thermoreversible hydrogels have the advantage of undergoing a sol/gel phase transition at specific temperatures. Thus, they are excellent candidates for biomedical applications such as drug delivery systems, wound healing coatings or cellular scaffolds. Although these hydrogels can be used in their natural form without further modification or chemical alteration, the original protein or polymer matrix is often strengthened by the use of a crosslinking agent to achieve a specific set of properties. In the case of gelatin fibril formation at low temperatures or the micellization of triblock copolymers in solution with temperature increase, the natural phase transition is modified when crosslinkers are introduced to alter the biohydrogels properties and, ultimately, disturb the system's equilibrium. By using spectroscopy techniques, rheology and cryo-imaging we investigated several biocompatible polymeric networks in their natural form as well as their engineered structures to better understand the mechanisms of gelation and artificial internal re-organization of the networks. Natural and synthetic biohydrogels were designed and their mechanical properties were characterized before imaging. Models that better describe the relationship between network configuration and resulting mechanical properties showed great agreement with experimental mesh size observations. Finally, a novel set of hybrid gels was developed and exhibited outstanding thermomechanical properties.

Ballistic Performance of Alimina/S-2 Glass-Reinforced Polymer-Matrix Composite Hybrid Lightweight Armor Against Armor Piercing (AP) and Non-AP Projectiles

DTIC Science & Technology

2007-01-01

and a phenolic -resin based polymeric matrix. Such armor panels offer superior protection against fragmented ballistic threats when compared to...database does not contain a material model for the HJ1 composite but provides a model for a Kevlar Fiber Reinforced Polymer (KFRP) containing 53 vol... phenolic resin and epoxy yield stresses and then with a ratio of the S-2 glass and aramid fibers volume fractions. To test the validity of the

E-beam-Cure Fabrication of Polymer Fiber/Matrix Composites for Multifunctional Radiation Shielding

NASA Technical Reports Server (NTRS)

Wilson, John W.; Jensen, Brian J.; Thibeault, Sheila A.; Hou, Tan-Hung; Saether, Erik; Glaessgen, Edward H.; Humes, Donald H.; Chang, Chie K.; Badavi, Francis F.; Kiefer, Rrichard L.;

Epoxy Nanocomposites Containing Zeolitic Imidazolate Framework-8.

PubMed

Liu, Cong; Mullins, Michael; Hawkins, Spencer; Kotaki, Masaya; Sue, Hung-Jue

2018-01-10

Zeolitic imidazole framework-8 (ZIF-8) is utilized as a functional filler and a curing agent in the preparation of epoxy nanocomposites. The imidazole group on the surface of the ZIF-8 initiates epoxy curing, resulting in covalent bonding between the ZIF-8 crystals and epoxy matrix. A substantial reduction in dielectric constant and increase in tensile modulus were observed. The implication of the present study for utilization of metal-organic framework to improve physical and mechanical properties of polymeric matrixes is discussed.

Fabrication of porous matrix membrane (PMM) using metal-organic framework as green template for water treatment.

PubMed

Lee, Jian-Yuan; Tang, Chuyang Y; Huo, Fengwei

2014-01-17

Pressure-driven membranes with high porosity can potentially be fabricated by removing template, such as low water stability metal-organic frameworks (MOFs) or other nanoparticles, in polymeric matrix. We report on the use of benign MOFs as green template to enhance porosity and interconnectivity of the water treatment membranes. Significantly enhanced separation performance was observed which might be attributed to the mass transfer coefficient of the substrate layer increased in ultrafiltration (UF) application.

Molecular Optics Nonlinear Optical Processes in Organic and Polymeric Crystals and Films. Part 1

DTIC Science & Technology

1991-11-01

Cycio-Octateraene ........... .93 Figure3.3; THG Dispersion Curve for Cyclo-Octateraene .... ......... 94 Figure3.4; Bloch Vector in Pauli Matrix Space... Jung , P. and Hanggi, P, Phys. Rev. Lett. 61, 11 (1989) I [90] Guckenheimer, J. and Holmes, P., Nonlinear Oscillations, Dynamical Sys- tems, and...identity matrix and Pauli matrices. p(t) = 1(1 + fr(t)F * 5) (3.5.6) I where the 3-vector FF is the linear coefficients of the Pauli matrices and is

Tough, high performance, addition-type thermoplastic polymers

NASA Technical Reports Server (NTRS)

Pater, Ruth H. (Inventor)

1992-01-01

A tough, high performance polyimide is provided by reacting a triple bond conjugated with an aromatic ring in a bisethynyl compound with the active double bond in a compound containing a double bond activated toward the formation of a Diels-Adler type adduct, especially a bismaleimide, a biscitraconimide, or a benzoquinone, or mixtures thereof. Addition curing of this product produces a high linear polymeric structure and heat treating the highly linear polymeric structure produces a thermally stable aromatic addition-type thermoplastic polyimide, which finds utility in the preparation of molding compounds, adhesive compositions, and polymer matrix composites.

Preparation of ellagic acid molecularly imprinted polymeric microspheres based on distillation-precipitation polymerization for the efficient purification of a crude extract.

PubMed

Zhang, Hua; Zhao, Shangge; Zhang, Lu; Han, Bo; Yao, Xincheng; Chen, Wen; Hu, Yanli

2016-08-01

Molecularly imprinted polymeric microspheres with a high recognition ability toward the template molecule, ellagic acid, were synthesized based on distillation-precipitation polymerization. The as-obtained polymers were characterized by scanning electron microscopy, infrared spectroscopy, and thermogravimetric analysis. Static, dynamic, and selective binding tests were adopted to study the binding properties and the molecular recognition ability of the prepared polymers for ellagic acid. The results indicated that the maximum static adsorption capacity of the prepared polymers toward ellagic acid was 37.07 mg/g and the adsorption equilibrium time was about 100 min when the concentration of ellagic acid was 40 mg/mL. Molecularly imprinted polymeric microspheres were also highly selective toward ellagic acid compared with its analogue quercetin. It was found that the content of ellagic acid in the pomegranate peel extract was enhanced from 23 to 86% after such molecularly imprinted solid-phase extraction process. This work provides an efficient way for effective separation and enrichment of ellagic acid from complex matrix, which is especially valuable in industrial production. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Phosphines bearing alkyne substituents: synthesis and hydrophosphination polymerization.

PubMed

Greenberg, Sharonna; Stephan, Douglas W

2009-09-07

A synthetic route is described for a series of phosphines bearing pendant alkyne substituents, from the conversion of BrC(6)H(2)R(2)C[triple bond]CR' (R = Me, i-Pr; R' = Ph, SiMe(3)) to [(mu-Br)Cu(Et(2)N)(2)PC(6)H(2)R(2)C[triple bond]CR'](2) and subsequently to Cl(2)PC(6)H(2)R(2)C[triple bond]CR' and H(2)PC(6)H(2)R(2)C[triple bond]CR'. Lithiation and subsequent alkylation yield the secondary phosphines R(H)PC(6)H(2)(i-Pr)(2)C[triple bond]CPh (R = CH(2)i-Pr, CH(2)Ph). Intermolecular hydrophosphination-polymerization is used to prepare the polymeric species [RPC(6)H(2)(i-Pr)(2)CH=CPh](n), which can then be sulfurized to give [RP(S)C(6)H(2)(i-Pr)(2)CH=CPh](n). The polymeric products were characterized by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and gel permeation chromatography. These data indicate a degree of polymerization (DP(n)) of up to 60. Discussion of the mechanism is augmented with gas-phase density functional theory calculations.

Prevalence of pesticides in postconsumer agrochemical polymeric packaging.

PubMed

Eras, J; Costa, J; Vilaró, F; Pelacho, A M; Canela-Garayoa, R; Martin-Closas, L

2017-02-15

Pesticide remains contained in agrochemical packaging waste are a source of uncontrolled risk for human health; they are also a quality feedstock for the plastic recycling industry. Many governments have recently started to establish laws and regulations to develop systems for recovering and recycling the polymeric packages used for pesticides. There is also a demand in having a procedure to control the suitability of the pesticide packages to be reused. We have developed a two-step operation process to assess the pesticide residues in agricultural containers made of a variety of polymeric matrices. The procedure is based on an extraction with a solvent mixture followed by UPLC-MS/MS determination. Solvents for neutral pesticides were selected considering the Hildebrand solubility (δ) of solvents and polymers together with those estimated for the pesticides. The proposed technique is effective in recovering imbibed pesticides in polymeric matrices. Also, a simplified extraction procedure has been tested to become a routine method for these wastes. We have found that in many cases a significant amount of pesticides remain into the polymeric matrix, even after a standardized cleaning; the impact of releasing these hazardous compounds into the environment is to be of further consideration. Copyright © 2016 Elsevier B.V. All rights reserved.

Recent advances of basic materials to obtain electrospun polymeric nanofibers for medical applications

NASA Astrophysics Data System (ADS)

Manea, L. R.; Hristian, L.; Leon, A. L.; Popa, A.

2016-08-01

The most important applications of electrospun polymeric nanofibers are by far those from biomedical field. From the biological point of view, almost all the human tissues and organs consist of nanofibroas structures. The examples include the bone, dentine, cartilage, tendons and skin. All these are characterized through different fibrous structures, hierarchically organized at nanometer scale. Electrospinning represents one of the nanotechnologies that permit to obtain such structures for cell cultures, besides other technologies, such as selfassembling and phase separation technologies. The basic materials used to produce electrospun nanofibers can be natural or synthetic, having polymeric, ceramic or composite nature. These materials are selected depending of the nature and structure of the tissue meant to be regenerated, namely: for the regeneration of smooth tissues regeneration one needs to process through electrospinning polymeric basic materials, while in order to obtain the supports for the regeneration of hard tissues one must mainly use ceramic materials or composite structures that permit imbedding the bioactive substances in distinctive zones of the matrix. This work presents recent studies concerning basic materials used to obtain electrospun polymeric nanofibers, and real possibilities to produce and implement these nanofibers in medical bioengineering applications.

Evaluating weathering of food packaging polyethylene-nano-clay composites: Release of nanoparticles and their impacts

EPA Science Inventory

Nano-fillers are increasingly incorporated into polymeric materials to improve the mechanical, barrier or other matrix properties of nanocomposites used for consumer and industrial applications. However, over the life cycle, these nanocomposites could degrade due to exposure to...

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes.

PubMed

Akhmetshina, Alsu A; Davletbaeva, Ilsiya M; Grebenschikova, Ekaterina S; Sazanova, Tatyana S; Petukhov, Anton N; Atlaskin, Artem A; Razov, Evgeny N; Zaripov, Ilnaz I; Martins, Carla F; Neves, Luísa A; Vorotyntsev, Ilya V

2015-12-30

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf₂N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N₂, NH₃, H₂S, and CO₂ gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF₆] and [emim][Tf₂N]. The modification of SILMs by nanosize silica particles leads to an increase of NH₃ separation relatively to CO₂ or H₂S.

Biochemical separations by continuous-bed chromatography.

PubMed

Tisch, T L; Frost, R; Liao, J L; Lam, W K; Remy, A; Scheinpflug, E; Siebert, C; Song, H; Stapleton, A

1998-08-07

Innovations in column-packing media for biomolecule purification have progressed from large spherical, porous polysaccharide beads to advanced polymeric supports. Continuous-bed technology is a radical new technology for chromatography based on the polymerization of advanced monomers and ionomers directly in the chromatographic column. The polymer chains form aggregates which coalesce into a dense, homogeneous network of interconnected nodules consisting of microparticles with an average diameter of 3000 A. The voids or channels between the nodules are large enough to permit a high hydrodynamic flow. Due to the high cross-linking of the polymer matrix, the surface of each nodule is nonporous yet the polymeric microparticles provide a very large surface area for high binding capacity. This paper will demonstrate the properties and advantages of using a continuous bed support for high resolution biomolecule separations at high flow-rates without sacrificing capacity.

Block copolymers for biomimetic composites

NASA Astrophysics Data System (ADS)

Calvert, Paul D.; Oner, Mualla; Burdon, Jeremy; Rieke, Peter C.; Farmer, Kelly

1993-07-01

Mineralized biological tissues can be regarded as composites where a fine reinforcement is laid down in a very controlled fashion within a tough polymeric matrix. Such materials include bone, antler, tooth enamel, mollusc shell, and crustacean shell. We have been exploring ways of forming similar structures by synthetic routes involving precipitation of reinforcing particles directly into a polymeric matrix. Part of this biomimetic approach requires polymer matrices which can exert a high degree of control over the mineralization process. Polymer gels have been formed from cross-linked methacrylates with various types of functionality within the gel. By incorporating calcium binding groups we have been producing gels which lead to preferential mineralization of the gel when it is incubated in a supersaturated solution of calcium oxalate or calcium carbonate. Similarly we have been incorporating silane groups within the gel in order to promote the deposition of silica in a gel body when it is immersed in a metastable solution of partly hydrolysed silicon alkoxides.

Environmental durability of polymer concrete

DOE Office of Scientific and Technical Information (OSTI.GOV)

Palmese, G.R.; Chawalwala, A.J.

1996-12-31

Over the past two decades, polymer concrete has increasingly been used for a number of applications including piping, machine bases, chemically resistant flooring, and bridge overlays. Currently, the use of polymer concrete as a wear surface for polymeric composite bridge decks is being investigated. Polymer concrete is a particulate composite comprised of mineral aggregate bound by a polymeric matrix. Such materials possess significantly higher mechanical properties than Portland cement concrete. However, the mechanical characteristics and environmental durability of polymer concrete are influenced by a number of factors. Among these are the selection of aggregate and resin, surface treatment, and curemore » conditions. In this work the influence of matrix selection and cure history on the environmental durability of polymer concrete was investigated. Particular attention was given to the effects of water on composite properties and to the mechanisms by which degradation occurs. The basalt-based polymer concrete systems investigated were susceptible to attack by water. Furthermore, results suggest that property loss associated with water exposure was primarily a result of interfacial weakening.« less

Photoinitiated Polymerization-Induced Self-Assembly (Photo-PISA): New Insights and Opportunities.

PubMed

Yeow, Jonathan; Boyer, Cyrille

2017-07-01

The polymerization-induced self-assembly (PISA) process is a useful synthetic tool for the efficient synthesis of polymeric nanoparticles of different morphologies. Recently, studies on visible light initiated PISA processes have offered a number of key research opportunities that are not readily accessible using traditional thermally initiated systems. For example, visible light mediated PISA (Photo-PISA) enables a high degree of control over the dispersion polymerization process by manipulation of the wavelength and intensity of incident light. In some cases, the final nanoparticle morphology of a single formulation can be modulated by simple manipulation of these externally controlled parameters. In addition, temporal (and in principle spatial) control over the Photo-PISA process can be achieved in most cases. Exploitation of the mild room temperature polymerizations conditions can enable the encapsulation of thermally sensitive therapeutics to occur without compromising the polymerization rate and their activities. Finally, the Photo-PISA process can enable further mechanistic insights into the morphological evolution of nanoparticle formation such as the effects of temperature on the self-assembly process. The purpose of this mini-review is therefore to examine some of these recent advances that have been made in Photo-PISA processes, particularly in light of the specific advantages that may exist in comparison with conventional thermally initiated systems.

Method and apparatus for pyrolysis of atactic polypropylene

DOEpatents

Staffin, H. Kenneth; Roaper, R. B.

1986-09-23

This invention relates to an apparatus and a method for pyrolytic decomposition of polymeric materials into lower molecular weight products involving the heat treatment of raw polymeric material within reactive conduits submerged in a fluidized bed furnace operated at pyrolizing temperatures.

EFFECT OF CONVENTIONAL AND EXPERIMENTAL GINGIVAL RETRACTION SOLUTIONS ON THE TENSILE STRENGTH AND INHIBITION OF POLYMERIZATION OF FOUR TYPES OF IMPRESSION MATERIALS

PubMed Central

Sábio, Sérgio; Franciscone, Paulo Afonso; Mondelli, José

2008-01-01

In the present study, two types of tests (tensile strength test and polymerization inhibition test) were performed to evaluate the physical and chemical properties of four impression materials [a polysulfide (Permlastic), a polyether (Impregum), a condensation silicone (Xantopren) and a polyvinylsiloxane (Aquasil)] when polymerized in contact with of one conventional (Hemostop) and two experimental (Vislin and Afrin) gingival retraction solutions. For the tensile strength test, the impression materials were mixed and packed into a steel plate with perforations that had residues of the gingival retraction solutions. After polymerization, the specimens were tested in tensile strength in a universal testing machine. For the polymerization inhibition test, specimens were obtained after taking impressions from a matrix with perforations that contained 1 drop of the gingival retraction solutions. Two independent examiners decided on whether or not impression material remnants remained unpolymerized, indicating interference of the chemical solutions. Based on the analysis of the results of both tests, the following conclusions were reached: 1. The tensile strength of the polysulfide decreased after contact with Hemostop and Afrin. 2. None of the chemical solutions inhibited the polymerization of the polysulfide; 3. The polyether presented lower tensile strength after polymerization in contact with the three gingival retraction agents; 4. The polyether had its polymerization inhibited only by Hemostop; 5. None of the chemical solutions affected the tensile strength of the condensation silicone; 6. Only Hemostop inhibited the polymerization of the condensation silicone; 7. The polyvinylsiloxane specimens polymerized in contact with Hemostop had significantly lower tensile strength; 8. Neither of the chemical solutions (Afrin and Vislin) affected the tensile strength of the polyvinylsiloxane and the condensation silicone; 9. Results of the tensile strength and polymerization inhibition tests suggest that Vislin can be used as substance of gingival retraction without affecting the tested properties of four impression materials. PMID:19089261

Effect of conventional and experimental gingival retraction solutions on the tensile strength and inhibition of polymerization of four types of impression materials.

PubMed

Sábio, Sérgio; Franciscone, Paulo Afonso; Mondelli, José

2008-01-01

In the present study, two types of tests (tensile strength test and polymerization inhibition test) were performed to evaluate the physical and chemical properties of four impression materials [a polysulfide (Permlastic), a polyether (Impregum), a condensation silicone (Xantopren) and a polyvinylsiloxane (Aquasil)] when polymerized in contact with of one conventional (Hemostop) and two experimental (Vislin and Afrin) gingival retraction solutions. For the tensile strength test, the impression materials were mixed and packed into a steel plate with perforations that had residues of the gingival retraction solutions. After polymerization, the specimens were tested in tensile strength in a universal testing machine. For the polymerization inhibition test, specimens were obtained after taking impressions from a matrix with perforations that contained 1 drop of the gingival retraction solutions. Two independent examiners decided on whether or not impression material remnants remained unpolymerized, indicating interference of the chemical solutions. Based on the analysis of the results of both tests, the following conclusions were reached: 1. The tensile strength of the polysulfide decreased after contact with Hemostop and Afrin. 2. None of the chemical solutions inhibited the polymerization of the polysulfide; 3. The polyether presented lower tensile strength after polymerization in contact with the three gingival retraction agents; 4. The polyether had its polymerization inhibited only by Hemostop; 5. None of the chemical solutions affected the tensile strength of the condensation silicone; 6. Only Hemostop inhibited the polymerization of the condensation silicone; 7. The polyvinylsiloxane specimens polymerized in contact with Hemostop had significantly lower tensile strength; 8. Neither of the chemical solutions (Afrin and Vislin) affected the tensile strength of the polyvinylsiloxane and the condensation silicone; 9. Results of the tensile strength and polymerization inhibition tests suggest that Vislin can be used as substance of gingival retraction without affecting the tested properties of four impression materials.

Noncovalent assembly. A rational strategy for the realization of chain-growth supramolecular polymerization.

PubMed

Kang, Jiheong; Miyajima, Daigo; Mori, Tadashi; Inoue, Yoshihisa; Itoh, Yoshimitsu; Aida, Takuzo

2015-02-06

Over the past decade, major progress in supramolecular polymerization has had a substantial effect on the design of functional soft materials. However, despite recent advances, most studies are still based on a preconceived notion that supramolecular polymerization follows a step-growth mechanism, which precludes control over chain length, sequence, and stereochemical structure. Here we report the realization of chain-growth polymerization by designing metastable monomers with a shape-promoted intramolecular hydrogen-bonding network. The monomers are conformationally restricted from spontaneous polymerization at ambient temperatures but begin to polymerize with characteristics typical of a living mechanism upon mixing with tailored initiators. The chain growth occurs stereoselectively and therefore enables optical resolution of a racemic monomer. Copyright © 2015, American Association for the Advancement of Science.

The effects of lactate and acid on articular chondrocytes function: Implications for polymeric cartilage scaffold design.

PubMed

Zhang, Xiaolei; Wu, Yan; Pan, Zongyou; Sun, Heng; Wang, Junjuan; Yu, Dongsheng; Zhu, Shouan; Dai, Jun; Chen, Yishan; Tian, Naifeng; Heng, Boon Chin; Coen, Noelle D; Xu, Huazi; Ouyang, Hongwei

2016-09-15

Poly (lactic-co-glycolic acid) (PLGA) and poly-l-lactate acid (PLLA) are biodegradable polymers widely utilized as scaffold materials for cartilage tissue engineering. Their acid degradation products have been widely recognized as being detrimental to cell function. However, the biological effects of lactate, rather than lactic acid, on chondrocytes have never been investigated. This is the major focus of this study. The amounts of lactate and the pH value (acid) of the PLGA and PLLA degradation medium were measured. The effects of PLGA and PLLA degradation medium, as well as different lactate concentrations and timing of exposure on chondrocytes proliferation and cartilage-specific matrix synthesis were investigated by various techniques including global gene expression profiling and gene knockdown experiments. It was shown that PLGA and PLLA degradation medium differentially regulated chondrocyte proliferation and matrix synthesis. Acidic pH caused by lactate inhibited chondrocyte proliferation and matrix synthesis. The effect of lactate on chondrocyte matrix synthesis was both time and dose dependent. A lactate concentration of 100mM and exposure duration of 8h significantly enhanced matrix synthesis. Lactate could also inhibit expression of cartilage matrix degradation genes in osteoarthritic chondrocytes, such as the major aggrecanase ADAMTS5, whilst promoting matrix synthesis simultaneously. Pulsed addition of lactate was shown to be more efficient in promoting COL2A1 expression. Global gene expression data and gene knock down experiments demonstrated that lactate promote matrix synthesis through up-regulation of HIF1A. These observed differential biological effects of lactate on chondrocytes would have implications for the future design of polymeric cartilage scaffolds. Lactic acid is a widely used substrate for polymers synthesis, PLGA and PLLA in particular. Although physical and biological modifications have been made on these polymers to make them be better cartilage scaffolds, little concern has been given on the biological effect of lactic acid, the main degradation product of these polymers, on chondrocytes. Our finding illustrates the differential biological function of lactate and acid on chondrocytes matrix synthesis. These results can facilitate future design of lactate polymers-based cartilage scaffolds. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Step Transfer-Addition and Radical-Termination (START) Polymerization of α,ω-Unconjugated Dienes under Irradiation of Blue LED Light.

PubMed

Xu, Tianchi; Yin, Hongnan; Li, Xiaohong; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

2017-07-01

A new polymerization method, termed as step transfer-addition and radical-termination, is developed for the step-growth radical polymerization of α,ω-unconjugated dienes under irradiation of visible light at room temperature (25 °C) for the first time. α,ω-Diiodoperfluoroalkane monomers (signified as A) are added onto α,ω-unconjugated dienes (signified as B) alternatively and efficiently with the generation of perfluorocarbon-containing alternating copolymers (AB) n . Based on the combined analyses of polymerization kinetics and NMR spectra ( 1 H and 19 F), the mechanism of the novel polymerization method, including the side reaction, is proposed. This novel polymerization method provides a new strategy not only for the step-growth radical polymerization of α,ω-unconjugated dienes but also for the construction of high molecular weight perfluorocarbon-containing alternating copolymers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ullmann-type coupling of brominated tetrathienoanthracene on copper and silver

NASA Astrophysics Data System (ADS)

Gutzler, Rico; Cardenas, Luis; Lipton-Duffin, Josh; El Garah, Mohamed; Dinca, Laurentiu E.; Szakacs, Csaba E.; Fu, Chaoying; Gallagher, Mark; Vondráček, Martin; Rybachuk, Maksym; Perepichka, Dmitrii F.; Rosei, Federico

2014-02-01

We report the synthesis of extended two-dimensional organic networks on Cu(111), Ag(111), Cu(110), and Ag(110) from thiophene-based molecules. A combination of scanning tunnelling microscopy and X-ray photoemission spectroscopy yields insight into the reaction pathways from single molecules towards the formation of two-dimensional organometallic and polymeric structures via Ullmann reaction dehalogenation and C-C coupling. The thermal stability of the molecular networks is probed by annealing at elevated temperatures of up to 500 °C. On Cu(111) only organometallic structures are formed, while on Ag(111) both organometallic and covalent polymeric networks were found to coexist. The ratio between organometallic and covalent bonds could be controlled by means of the annealing temperature. The thiophene moieties start degrading at 200 °C on the copper surface, whereas on silver the degradation process becomes significant only at 400 °C. Our work reveals how the interplay of a specific surface type and temperature steers the formation of organometallic and polymeric networks and describes how these factors influence the structural integrity of two-dimensional organic networks.We report the synthesis of extended two-dimensional organic networks on Cu(111), Ag(111), Cu(110), and Ag(110) from thiophene-based molecules. A combination of scanning tunnelling microscopy and X-ray photoemission spectroscopy yields insight into the reaction pathways from single molecules towards the formation of two-dimensional organometallic and polymeric structures via Ullmann reaction dehalogenation and C-C coupling. The thermal stability of the molecular networks is probed by annealing at elevated temperatures of up to 500 °C. On Cu(111) only organometallic structures are formed, while on Ag(111) both organometallic and covalent polymeric networks were found to coexist. The ratio between organometallic and covalent bonds could be controlled by means of the annealing temperature. The thiophene moieties start degrading at 200 °C on the copper surface, whereas on silver the degradation process becomes significant only at 400 °C. Our work reveals how the interplay of a specific surface type and temperature steers the formation of organometallic and polymeric networks and describes how these factors influence the structural integrity of two-dimensional organic networks. Electronic supplementary information (ESI) available: Additional STM data and DFT results. See DOI: 10.1039/c3nr05710k

The preparations of novel cellulose/phenylboronic acid composite intelligent bio-hydrogel and its glucose, pH-responsive behaviors.

PubMed

Peng, Huafeng; Ning, Xiaoyu; Wei, Gang; Wang, Shaopeng; Dai, Guoliang; Ju, Anqi

2018-09-01

Novel intelligent cellulose/4-vinyl-phenylboronic acid (VPBA) composite bio-hydrogels with glucose and pH-responsiveness were successfully prepared via electron beam irradiation technology at room temperature. The composites were characterized by Fourier transform infrared spectrum (FT-IR) and X-ray photoelectron spectroscopy (XPS). The electron beam irradiation results in the appearance of carbonyl in the polymerization of 4-ethenyl-phenylboronic acid, grafting and cross linking reaction in composites, and a novel composite hydrogel was formed between the poly-4-ethenyl-phenylboronic acid and cellulose matrix. By means of the incorporation of phenylboronic acid groups, the composite hydrogels with pH and glucose responsive properties was produced, and glucose responsive properties were investigated by the self-regulation of insulin release of composite hydrogel through a serial glucose solution with different concentrations, which is having great potential applications in many fields. Copyright © 2018 Elsevier Ltd. All rights reserved.

Process for introducing electrical conductivity into high-temperature polymeric materials

DOEpatents

Liepins, R.; Jorgensen, B.S.; Liepins, L.Z.

1993-12-21

High-temperature electrically conducting polymers are described. The in situ reactions: AgNO[sub 3] + RCHO [yields] Ag + RCOOH and R[sub 3]M [yields] M + 3R, where M=Au or Pt have been found to introduce either substantial bulk or surface conductivity in high-temperature polymers. The reactions involving the R[sub 3]M were caused to proceed thermally suggesting the possibility of using laser means for initiating such reactions in selected areas or volumes of the polymeric materials. The polymers successfully investigated to date are polyphenylquinoxaline, polytolylquinoxaline, polyquinoline, polythiazole, and pyrone.

Process for introducing electrical conductivity into high-temperature polymeric materials

DOEpatents

Liepins, Raimond; Jorgensen, Betty S.; Liepins, Leila Z.

1993-01-01

High-temperature electrically conducting polymers. The in situ reactions: AgNO.sub.3 +RCHO.fwdarw.Ag.degree.+RCOOH and R.sub.3 M.fwdarw.M.degree.+3R, where M=Au or Pt have been found to introduce either substantial bulk or surface conductivity in high-temperature polymers. The reactions involving the R.sub.3 M were caused to proceed thermally suggesting the possibility of using laser means for initiating such reactions in selected areas or volumes of the polymeric materials. The polymers successfully investigated to date are polyphenylquinoxaline, polytolylquinoxaline, polyquinoline, polythiazole, and pyrrone.

Process for introducing electrical conductivity into high-temperature polymeric materials

DOEpatents

Liepins, Raimond; Jorgensen, Betty S.; Liepins, Leila Z.

1989-01-01

High-temperature electrically conducting polymers. The in situ reactions: AgNO.sub.3 +RCHO.fwdarw.AG.sup.0 +RCOOH and R.sub.3 M.fwdarw.M.sup.0 3R, where M=Au or Pt have been found to introduce either substantial bulk or surface conductivity in high-temperature polymers. The reactions involving the R.sub.3 M were caused to proceed thermally suggesting the possibility of using laser means for initiating such reactions in selected areas or volumes of the polymeric materials. The polymers successfully investigated to date are polyphenylquinoxaline, polytolylquinoxaline, polyquinoline, polythiazole, and pyrrone.

Process for introducing electrical conductivity into high-temperature polymeric materials

DOEpatents

Liepins, R.; Jorgensen, B.S.; Liepins, L.Z.

1987-08-27

High-temperature electrically conducting polymers. The in situ reactions: AgNO/sub 3/ + RCHO ..-->.. Ag/sup 0/ + RCOOH and R/sub 3/M ..-->.. M/sup 0/ + 3R, where M = Au or Pt have been found to introduce either substantial bulk or surface conductivity in high- temperature polymers. The reactions involving the R/sub 3/M were caused to proceed thermally suggesting the possibility of using laser means for initiating such reactions in selected areas or volumes of the polymeric materials. The polymers successfully investigated to date are polyphenylquinoxaline, polytolylquinoxaline, polyquinoline, polythiazole, and pyrrone. 3 tabs.

Conformational effects on cationization of poly(ethylene glycol) by alkali metal ions in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

NASA Astrophysics Data System (ADS)

Shimada, Kayori; Matsuyama, Shigetomo; Saito, Takeshi; Kinugasa, Shinichi; Nagahata, Ritsuko; Kawabata, Shin-Ichirou

2005-12-01

Conformational effects of polymer chains on matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) were studied by using an equimolar mixture of uniform poly(ethylene glycol)s (PEGs) and by molecular dynamics simulations. Uniform PEGs with degrees of polymerization n = 8-39 were separated from commercial PEG samples by preparative supercritical fluid chromatography. MALDI-TOFMS spectra of an equimolar mixture of the uniform PEGs in aqueous ethanol were measured by adding a mixture of 2,5-dihydroxybenzoic acid (as a matrix reagent) and five alkali metal chlorides (LiCl, NaCl, KCl, RbCl, and CsCl). After optimization of the matrix concentration and laser power, five types of adduct cationized by Li+, Na+, K+, Rb+, and Cs+ could be identified simultaneously in the same spectrum. In the lower molecular-mass region around 103, the spectral intensity increase rapidly with increasing molecular mass of PEG; this rapid increase in the spectral intensity started at a lower molecular mass for smaller adduct cations. Molecular dynamics simulations were used to calculated the affinity of PEG for the adduct cations. These experimental and simulated results showed that the observed spectral intensities in MALDI-TOFMS were markedly affected by the species of adduct cations and the degree of polymerization of the PEG, and that they were dependent on the stability of the PEG-cation complex.

Characterization of extracellular polymeric matrix, and treatment of Fusobacterium nucleatum and Porphyromonas gingivalis biofilms with DNase I and proteinase K.

PubMed

Ali Mohammed, Marwan Mansoor; Nerland, Audun H; Al-Haroni, Mohammed; Bakken, Vidar

2013-01-01

Biofilms are organized communities of microorganisms embedded in a self-produced extracellular polymeric matrix (EPM), often with great phylogenetic variety. Bacteria in the subgingival biofilm are key factors that cause periodontal diseases; among these are the Gram-negative bacteria Fusobacterium nucleatum and Porphyromonas gingivalis. The objectives of this study were to characterize the major components of the EPM and to test the effect of deoxyribonuclease I (DNase I) and proteinase K. F. nucleatum and P. gingivalis bacterial cells were grown in dynamic and static biofilm models. The effects of DNase I and proteinase K enzymes on the major components of the EPM were tested during biofilm formation and on mature biofilm. Confocal laser scanning microscopy was used in observing biofilm structure. Proteins and carbohydrates were the major components of the biofilm matrix, and extracellular DNA (eDNA) was also present. DNase I and proteinase K enzymes had little effect on biofilms in the conditions used. In the flow cell, F. nucleatum was able to grow in partially oxygenated conditions while P. gingivalis failed to form biofilm alone in similar conditions. F. nucleatum supported the growth of P. gingivalis when they were grown together as dual species biofilm. DNase I and proteinase K had little effect on the biofilm matrix in the conditions used. F. nucleatum formed biofilm easily and supported the growth of P. gingivalis, which preferred anaerobic conditions.

Mapping the Dynamics of Shear Stress—Induced Structural Changes in Endothelial Cells

PubMed Central

Mott, Rosalind E.; Helmke, Brian P.

2009-01-01

Hemodynamic shear stress regulates endothelial cell biochemical processes that govern cytoskeletal contractility, focal adhesion dynamics, and extracellular matrix assembly. Since shear stress causes rapid strain focusing at discrete locations in the cytoskeleton, we hypothesized that shear stress coordinately alters structural dynamics in the cytoskeleton, focal adhesion sites, and extracellular matrix on a time scale of minutes. Using multi-wavelength 4-D fluorescence microscopy, we measured the displacement of rhodamine-fibronectin and of GFP-labeled actin, vimentin, paxillin, and/or vinculin in aortic endothelial cells before and after onset of steady unidirectional shear stress. In the cytoskeleton, the onset of shear stress increased actin polymerization into lamellipodia, altered the angle of lateral displacement of actin stress fibers and vimentin filaments, and decreased centripetal remodeling of actin stress fibers in both subconfluent and confluent cell layers. Shear stress induced the formation of new focal complexes and reduced the centripetal remodeling of focal adhesions in regions of new actin polymerization. The structural dynamics of focal adhesions and the fibronectin matrix varied with cell density. In subconfluent cell layers, shear stress onset decreased the displacement of focal adhesions and fibronectin fibrils. In confluent monolayers, the direction of fibronectin and focal adhesion displacement shifted significantly towards the downstream direction within one minute after onset of shear stress. These spatially coordinated rapid changes in the structural dynamics of cytoskeleton, focal adhesions, and extracellular matrix are consistent with focusing of mechanical stress and/or strain near major sites of shear stress-mediated mechanotransduction. PMID:17855768

Hydrophobic Modification of Layered Clays and Compatibility for Epoxy Nanocomposites

PubMed Central

Lin, Jiang-Jen; Chan, Ying-Nan; Lan, Yi-Fen

2010-01-01

Recent studies on the intercalation and exfoliation of layered clays with polymeric intercalating agents involving poly(oxypropylene)-amines and the particular uses for epoxy nanocomposites are reviewed. For intercalation, counter-ionic exchange reactions of clays including cationic layered silicates and anionic Al-Mg layered double hydroxide (LDH) with polymeric organic ions afforded organoclays led to spatial interlayer expansion from 12 to 92 Å (X-ray diffraction) as well as hydrophobic property. The inorganic clays of layered structure could be modified by the poly(oxypropylene)amine-salts as the intercalating agents with molecular weights ranging from 230 to 5,000 g/mol. Furthermore, natural montmorillonite (MMT) clay could be exfoliated into thin layer silicate platelets (ca. 1 nm thickness) in one step by using polymeric types of exfoliating agents. Different lateral dimensions of MMT, synthetic fluorinated Mica and LDH clays had been cured into epoxy nanocomposites. The hydrophobic amine-salt modification resulting in high spacing of layered or exfoliation of individual clay platelets is the most important factor for gaining significant improvements of properties. In particular, these modified clays were reported to gain significant improvements such as reduced coefficient of thermal expansion (CTE), enhanced thermal stability, and hardness. The utilization of these layered clays for initiating the epoxy self-polymerization was also reported to have a unique compatibility between clay and organic resin matrix. However, the matrix domain lacks of covalently bonded crosslink and leads to the isolation of powder material. It is generally concluded that the hydrophobic expansion of the clay inter-gallery spacing is the crucial step for enhancing the compatibility and the ultimate preparation of the advanced epoxy materials.

Atomic Force Microscopy (AFM) for In-Situ Biofilm Surface Characterization during Free Chlorine and Monochloramine Exposure

EPA Science Inventory

Drinking water distribution system biofilm are attached to pipe walls and found in sediments. These biofilms are complex and contain a variety of microorganisms embedded in a matrix with extracellular polymeric substances (EPS), providing protection from disinfection. Without pro...

Mechanical, thermal, and moisture properties of plastics with bean as filler

USDA-ARS?s Scientific Manuscript database

Experiments on polymers using beans as fillers are reported herein. We are looking for desirable mechanical, thermal and moisture properties at economical costs. Poly(lactic acid) (PLA) is studied as the polymeric matrix because it is available and biodegradable. Although the physical properties are...

Method and apparatus for pyrolysis of atactic polypropylene

DOEpatents

Staffin, H.K.; Roaper, R.B.

1986-09-23

This invention relates to an apparatus and a method for pyrolytic decomposition of polymeric materials into lower molecular weight products involving the heat treatment of raw polymeric material within reactive conduits submerged in a fluidized bed furnace operated at pyrolyzing temperatures. 1 fig.

Pharmaceutical acrylic beads obtained by suspension polymerization containing cellulose nanowhiskers as excipient for drug delivery.

PubMed

Villanova, J C O; Ayres, E; Carvalho, S M; Patrício, P S; Pereira, F V; Oréfice, R L

2011-03-18

Direct compression is one of the most popular techniques to prepare tablets but only a few commercial excipients are well adapted for this process into controlled release formulations. In the last years, the introduction of new materials for drug delivery matrix tablets has become more important. This paper evaluated the physicochemical and flow properties of new polymeric excipient of ethyl acrylate, methyl methacrylate and butyl metacrylate, synthesized by suspension polymerization using cellulose nanowhiskers as co-stabilizer, to be used as direct compression for modified release tablets. Infrared spectroscopy (FTIR) confirmed the success of the copolymerization reaction. Scanning electron microscopy (SEM) showed that excipient was obtained how spherical beads. Thermal properties of the beads were characterized by thermogravimetric (TG) analysis. Particle size analysis of the beads with cellulose nanowhiskers (CNWB) indicated that the presence of the nanowhiskers led to a reduction of particle size and to a narrower size distribution. In vitro test showed that the nanowhiskers and beads produced are nontoxic. Parameters such as Hausner ratio, Carr's index and cotangent of angle α were employed to characterize the flow properties of CNWB beads. Furthermore, the beads are used to produce tablets by direct compression contained propranolol hydrochloride as model drug. Dissolution tests performed suggested that beads could be used as excipient in matrix tablets with a potential use in drug controlled release. Copyright © 2011 Elsevier B.V. All rights reserved.

Design of a Novel Two-Component Hybrid Dermal Scaffold for the Treatment of Pressure Sores.

PubMed

Sharma, Vaibhav; Kohli, Nupur; Moulding, Dale; Afolabi, Halimat; Hook, Lilian; Mason, Chris; García-Gareta, Elena

2017-11-01

The aim of this study is to design a novel two-component hybrid scaffold using the fibrin/alginate porous hydrogel Smart Matrix combined to a backing layer of plasma polymerized polydimethylsiloxane (Sil) membrane to make the fibrin-based dermal scaffold more robust for the treatment of the clinically challenging pressure sores. A design criteria are established, according to which the Sil membranes are punched to avoid collection of fluid underneath. Manual peel test shows that native silicone does not attach to the fibrin/alginate component while the plasma polymerized silicone membranes are firmly bound to fibrin/alginate. Structural characterization shows that the fibrin/alginate matrix is intact after the addition of the Sil membrane. By adding a Sil membrane to the original fibrin/alginate scaffold, the resulting two-component scaffolds have a significantly higher shear or storage modulus G'. In vitro cell studies show that dermal fibroblasts remain viable, proliferate, and infiltrate the two-component hybrid scaffolds during the culture period. These results show that the design of a novel two-component hybrid dermal scaffold is successful according to the proposed design criteria. To the best of the authors' knowledge, this is the first study that reports the combination of a fibrin-based scaffold with a plasma-polymerized silicone membrane. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic effect investigation of a potentiometric sensor for urea and surface morphology observation of entrapped urease/polypyrrole matrix.

PubMed

Syu, Mei-Jywan; Chang, Yu-Sung

2009-04-15

Potentio-dynamic polymerization of buffered urease and pyrrole monomer onto carbon papers was conducted to fabricate an immobilized urease electrode for measuring the urea concentration. To use carbon paper as the substrate for the electro-growth of polypyrrole matrix not only created sufficient adhesion of the conducting polymer layer but also provided superior entrapment of urease enzymes. The potentiometric response corresponding to ammonia, the product formed from the urease catalyzed urea reaction, was employed for the urea concentration measurement. Scanning electron microscopic photographs showed that the polypyrrole matrix deposited on the carbon papers appeared to be of a cylindrical nanotube shape. The charge density applied in the polymerization was found to affect the potentiometric response while the potential-scanning rate showed minor influence. The composite electrodes had high sensitivity in urea detection, showing a response linear to the logarithm of the urea concentration in the range of 10(-3) to 10 mM. The detection of urea solution prepared in water and buffer was also compared. Ionic effect on the sensing of urea solution was investigated. By comparing the data reported in literature, the urease/polypyrrole/carbon paper electrode developed in this work showed superior long-term stability and reusability. The detection of urea in serum was also well performed.

Associative charge transfer reactions. Temperature effects and mechanism of the gas-phase polymerization of propene initiated by a benzene radical cation.

PubMed

Ibrahim, Yehia; Meot-Ner Mautner, Michael; El-Shall, M Samy

2006-07-13

In associative charge transfer (ACT) reactions, a core ion activates ligand molecules by partial charge transfer. The activated ligand polymerizes, and the product oligomer takes up the full charge from the core ion. In the present system, benzene(+*) (Bz(+*)) reacts with two propene (Pr) molecules to form a covalently bonded ion, C(6)H(6)(+*) + 2 C(3)H(6) --> C(6)H(12)(+*) + C(6)H(6). The ACT reaction is activated by a partial charge transfer from Bz(+*) to Pr in the complex, and driven to completion by the formation of a covalent bond in the polymerized product. An alternative channel forms a stable association product (Bz.Pr)(+*), with an ACT/association product ratio of 60:40% that is independent of pressure and temperature. In contrast to the Bz(+*)/propene system, ACT polymerization is not observed in the Bz(+*)/ethylene (Et) system since charge transfer in the Bz(+*)(Et) complex is inefficient to activate the reaction. The roles of charge transfer in these complexes are verified by ab initio calculations. The overall reaction of Bz(+*) with Pr follows second-order kinetics with a rate constant of k (304 K) = 2.1 x 10(-12) cm(3) s(-1) and a negative temperature coefficient of k = aT(-5.9) (or an activation energy of -3 kcal/mol). The kinetic behavior is similar to sterically hindered reactions and suggests a [Bz(+*) (Pr)]* activated complex that proceeds to products through a low-entropy transition state. The temperature dependence shows that ACT reactions can reach a unit collision efficiency below 100 K, suggesting that ACT can initiate polymerization in cold astrochemical environments.

Spatially controlled, in situ synthesis of polymers

DOEpatents

Caneba, Gerard T.; Tirumala, Vijaya Raghavan; Mancini, Derrick C.; Wang, Hsien-Hau

2005-03-22

An in situ polymer microstructure formation method. The monomer mixture is polymerized in a solvent/precipitant through exposure to ionizing radiation in the absence any chemical mediators. If an exposure mask is employed to block out certain regions of the radiation cross section, then a patterned microstructure is formed. The polymerization mechanism is based on the so-called free-radical retrograde-precipitation polymerization process, in which polymerization occurs while the system is phase separating above the lower critical solution temperature. This method was extended to produce a crosslinked line grid-pattern of poly (N-isopropylacrylamide), which has been known to have thermoreversible properties.

Effect of shape on bone cement polymerization time in knee joint replacement surgery

PubMed Central

Yoon, Jung-Ro; Ko, Young-Rok; Shin, Young-Soo

2018-01-01

Abstract Background: Although many factors are known to influence the polymerization time of bone cement, it remains unclear which bone cement shape predicts the precise polymerization time. The purpose of this study was to investigate whether different cement shapes influenced polymerization time and to identify the relationship between cement shape and ambient operating theater temperature, relative humidity, and equilibration time. Methods: Samples were gathered prospectively from 237 patients undergoing primary total knee arthroplasty. The cement components were made into 2 different shapes: lump and pan. The time at which no macroscopic indentation of both cement models was possible was recorded as the polymerization time. Results: There was no significant difference between hand mixing (lump shape: 789.3 ± 128.4 seconds, P = .591; pan shape: 899.3 ± 152.2 seconds, P = .584) and vacuum mixing (lump shape: 780.2 ± 131.1 seconds, P = .591; pan shape: 909.9 ± 143.3 seconds, P = .584) in terms of polymerization time. Conversely, the polymerization time was significantly shorter for Antibiotic Simplex (lump shape: 757.4 ± 114.9 seconds, P = .001; pan shape: 879.5 ± 125.0 seconds, P < .001) when compared with Palacos R+G (lump shape: 829.0 ± 139.3 seconds, P = .001; pan shape: 942.9 ± 172.0 seconds, P < .001). Polymerization time was also significantly longer (P < .001) for the pan shape model (904 ± 148.0 seconds) when compared with the lump shape model (785.2 ± 129.4 seconds). In addition, the polymerization time decreased with increasing temperature (lump shape: R2 = 0.334, P < .001; pan shape: R2 = 0.375, P < .001), humidity (lump shape: R2 = 0.091, P < .001; pan shape: R2 = 0.106, P < .001), and equilibration time (lump shape: R2 = 0.073, P < .001; pan shape: R2 = 0.044, P < .001). Conclusions: The polymerization time was equally affected by temperature, relative humidity, and equilibration time regardless of bone cement shape. Furthermore, the pan shape model better reflected the cement polymerization time between implant and bone compared with the lump shape model. The current findings suggest that, clinically, constant pressure with the knee in <45° of flexion needs to be applied until remaining pan shaped cement is completely polymerized. PMID:29703041

A novel role for the integrin-binding III-10 module in fibronectin matrix assembly.

PubMed

Hocking, D C; Smith, R K; McKeown-Longo, P J

1996-04-01

Fibronectin matrix assembly is a cell-dependent process which is upregulated in tissues at various times during development and wound repair to support the functions of cell adhesion, migration, and differentiation. Previous studies have demonstrated that the alpha 5 beta 1 integrin and fibronectin's amino terminus and III-1 module are important in fibronectin polymerization. We have recently shown that fibronectin's III-1 module contains a conformationally sensitive binding site for fibronectin's amino terminus (Hocking, D.C., J. Sottile, and P.J. McKeown-Longo. 1994. J. Biol. Chem. 269: 19183-19191). The present study was undertaken to define the relationship between the alpha 5 beta 1 integrin and fibronectin polymerization. Solid phase binding assays using recombinant III-10 and III-1 modules of human plasma fibronectin indicated that the III-10 module contains a conformation-dependent binding site for the III-1 module of fibronectin. Unfolded III-10 could support the formation of a ternary complex containing both III-1 and the amino-terminal 70-kD fragment, suggesting that the III-1 module can support the simultaneous binding of III-10 and 70 kD. Both unfolded III-10 and unfolded III-1 could support fibronectin binding, but only III-10 could promote the formation of disulfide-bonded multimers of fibronectin in the absence of cells. III-10-dependent multimer formation was inhibited by both the anti-III-1 monoclonal antibody, 9D2, and amino-terminal fragments of fibronectin. A fragment of III-10, termed III-10/A, was able to block matrix assembly in fibroblast monolayers. Similar results were obtained using the III-10A/RGE fragment, in which the RGD site had been mutated to RGE, indicating that III-I0/A was blocking matrix assembly by a mechanism distinct from disruption of integrin binding. Texas red-conjugated recombinant III-1,2 localized to beta 1-containing sites of focal adhesions on cells plated on fibronectin or the III-9,10 modules of fibronectin. Monoclonal antibodies against the III-1 or the III-9,10 modules of fibronectin blocked binding of III-1,2 to cells without disrupting focal adhesions. These data suggest that a role of the alpha 5 beta 1 integrin in matrix assembly is to regulate a series of sequential self-interactions which result in the polymerization of fibronectin.

Polyurethane acrylate networks including cellulose nanocrystals: a comparison between UV and EB- curing

NASA Astrophysics Data System (ADS)

Furtak-Wrona, K.; Kozik-Ostrówka, P.; Jadwiszczak, K.; Maigret, J. E.; Aguié-Béghin, V.; Coqueret, X.

2018-01-01

A water-based polyurethane (PUR) acrylate water emulsion was selected as a radiation curable matrix for preparing nanocomposites including cellulose nanocrystals (CNC) prepared by controlled hydrolysis of Ramie fibers. Cross-linking polymerization of samples prepared in the form of films or of 1 mm-thick bars was either initiated by exposure to the 395 nm light of a high intensity LED lamp or by treatment with low energy electron beam (EB). The conversion level of acrylate functions in samples submitted to increasing radiation doses was monitored by Fourier Transform Infrared Spectroscopy (FTIR). Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA) were used to characterize changes in the glass transition temperature of the PUR-CNC nanocomposites as a function of acrylate conversion and of CNC content. Micromechanical testing indicates the positive effect of 1 wt% CNC on Young's modulus and on the tensile strength at break (σ) of cured nanocomposites. The presence of CNC in the PUR acrylate matrix was shown to double the σ value of the nanocomposite cured to an acrylate conversion level of 85% by treatment with a 25 kGy dose under EB, whereas no increase of σ was observed in UV-cured samples exhibiting the same acrylate conversion level. The occurrence of grafting reactions inducing covalent linkages between the polysaccharide nanofiller and the PUR acrylate matrix during the EB treatment is advanced as an explanation to account for the improvement observed in samples cured under ionizing radiation.

Synergistic Effects of Physical Aging and Damage on Long-Term Behavior of Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Brinson, L. Cate

1999-01-01

The research consisted of two major parts, first modeling and simulation of the combined effects of aging and damage on polymer composites and secondly an experimental phase examining composite response at elevated temperatures, again activating both aging and damage. For the simulation, a damage model for polymeric composite laminates operating at elevated temperatures was developed. Viscoelastic behavior of the material is accounted for via the correspondence principle and a variational approach is adopted to compute the temporal stresses within the laminate. Also, the effect of physical aging on ply level stress and on overall laminate behavior is included. An important feature of the model is that damage evolution predictions for viscoelastic laminates can be made. This allows us to track the mechanical response of the laminate up to large load levels though within the confines of linear viscoelastic constitutive behavior. An experimental investigation of microcracking and physical aging effects in polymer matrix composites was also pursued. The goal of the study was to assess the impact of aging on damage accumulation, in ten-ns of microcracking, and the impact of damage on aging and viscoelastic behavior. The testing was performed both at room and elevated temperatures on [+/- 45/903](sub s) and [02/903](sub s) laminates, both containing a set of 90 deg plies centrally located to facilitate investigation of microcracking. Edge replication and X-ray-radiography were utilized to quantify damage. Sequenced creep tests were performed to characterize viscoelastic and aging parameters. Results indicate that while the aging times studied have limited ]Influence on damage evolution, elevated temperature and viscoelastic effects have a profound effect on the damage mode seen. Some results are counterintuitive, including the lower strain to failure for elevated temperature tests and the catastrophic failure mode observed for the [+/- 45/9O3](sub s), specimens. The fracture toughness for transverse cracks increases with increasing temperature for both systems: transverse cracking was completely absent prior to failure in [+/- 45/903](sub s), and was suppressed for [02/903](sub s). No significant effect of damage on aging or viscoelastic parameters was observed.

Smart polyaniline nanoparticles with thermal and photothermal sensitivity

NASA Astrophysics Data System (ADS)

Bongiovanni Abel, Silvestre; Molina, María A.; Rivarola, Claudia R.; Kogan, Marcelo J.; Barbero, Cesar A.

2014-12-01

Conductive polyaniline nanoparticles (PANI NPs) are synthesized by oxidation of aniline with persulfate in acid media, in the presence of polymeric stabilizers: polyvinilpyrrolidone (PVP), poly(N-isopropylacrylamide) (PNIPAM), and hydroxylpropylcellulose (HPC). It is observed that the size of the nanoparticles obtained depends on the polymeric stabilizer used, suggesting a mechanism where the aggregation of polyaniline molecules is arrested by adsorption of the polymeric stabilizer. Indeed, polymerization in the presence of a mixture of two polymers having different stabilizing capacity (PVP and PNIPAM) allows tuning of the size of the nanoparticles. Stabilization with biocompatible PVP, HPC and PNIPAM allows use of the nanoparticle dispersions in biological applications. The nanoparticles stabilized by thermosensitive polymers (PNIPAM and HPC) aggregate when the temperature exceeds the phase transition (coil to globule) temperature of each stabilizer (Tpt = 32 °C for PNIPAM or Tpt = 42 °C for HPC). This result suggests that an extended coil form of the polymeric stabilizer is necessary to avoid aggregation. The dispersions are reversibly restored when the temperature is lowered below Tpt. In that way, the effect could be used to separate the nanoparticles from soluble contaminants. On the other hand, the PANI NPs stabilized with PVP are unaffected by the temperature change. UV-visible spectroscopy measurements show that the nanoparticle dispersion changes their spectra with the pH of the external solution, suggesting that small molecules can easily penetrate the stabilizer shell. Near infrared radiation is absorbed by PANI NPs causing an increase of their temperature which induces the collapse of the thermosensitive polymer shell and aggregation of the NPs. The effect reveals that it is possible to locally heat the nanoparticles, a phenomenon that can be used to destroy tumor cells in cancer therapy or to dissolve protein aggregates of neurodegenerative diseases (e.g. Alzheimer). Moreover, the long range control of aggregation can be used to modulate the nanoparticle residence inside biological tissues.

The effect of phase change materials on the frontal polymerization of a triacrylate

NASA Astrophysics Data System (ADS)

Viner, Veronika G.; Pojman, John A.; Golovaty, Dmitry

2010-06-01

The production of smoke and fumes is a major obstacle to the practical use of thermal frontal polymerization. The front temperature and the amount of smoking can be reduced by adding inert fillers, such as clay and silica, to the reactive mixture. Here we investigate the possibility of incorporating inert materials that melt (so-called phase change materials) to the mixture. By performing both experiments and mathematical modeling, we demonstrate that, in addition to the standard parameters of frontal polymerization, the front temperature and velocity depend on the melting point and heat of fusion of the phase change material. We use the method of matched asymptotic expansions to develop an explicit expression for the velocity of the reaction front. The expression demonstrates that the behavior of the front is determined by the difference between the reaction temperature and the melting temperature, with the front being slower and cooler if melting occurs farther ahead of the reaction front. The theoretical trends are hard to confirm directly because different characteristics of the phase change material cannot be varied separately.

Glass Fiber Reinforced Polypropylene Mechanical Properties Enhancement by Adhesion Improvement

PubMed Central

Etcheverry, Mariana; Barbosa, Silvia E.

2012-01-01

Glass fibers (GF) are the reinforcement agent most used in polypropylene (PP) based composites, as they have good balance between properties and costs. However, their final properties are mainly determined by the strength and stability of the polymer-fiber interphase. Fibers do not act as an effective reinforcing material when the adhesion is weak. Also, the adhesion between phases can be easily degraded in aggressive environmental conditions such as high temperatures and/or elevated moisture, and by the stress fields to which the material may be exposed. Many efforts have been done to improve polymer-glass fiber adhesion by compatibility enhancement. The most used techniques include modifications in glass surface, polymer matrix and/or both. However, the results obtained do not show a good costs/properties improvement relationship. The aim of this work is to perform an accurate analysis regarding methods for GF/PP adhesion improvement and to propose a new route based on PP in-situ polymerization onto fibers. This route involves the modification of fibers with an aluminum alkyl and hydroxy-α-olefin and from there to enable the growth of the PP chains using direct metallocenic copolymerization. The adhesion improvements were further proved by fragmentation test, as well as by mechanical properties measurements. The strength and toughness increases three times and the interfacial strength duplicates in PP/GF composites prepared with in-situ polymerized fibers. PMID:28817025

Interaction of Pb(II) and biofilm associated extracellular polymeric substances of a marine bacterium Pseudomonas pseudoalcaligenes NP103

NASA Astrophysics Data System (ADS)

Kumari, Supriya; Mangwani, Neelam; Das, Surajit

2017-02-01

Three-dimensional excitation-emission matrix (3D EEM) fluorescence spectroscopy and attenuated total reflectance fourier-transformed infrared spectroscopy (ATR-FTIR) was used to evaluate the interaction of biofilm associated extracellular polymeric substances (EPS) of a marine bacterium Pseudomonas pseudoalcaligenes NP103 with lead [Pb(II)]. EEM fluorescence spectroscopic analysis revealed the presence of one protein-like fluorophore in the EPS of P. pseudoalcaligenes NP103. Stern-Volmer equation indicated the existence of only one binding site (n = 0.789) in the EPS of P. pseudoalcaligenes NP103. The interaction of Pb(II) with EPS was spontaneous at room temperature (Δ G = - 2.78 kJ/K/mol) having binding constant (Kb) of 2.59 M- 1. ATR-FTIR analysis asserted the involvement of various functional groups such as sulphydryl, phosphate and hydroxyl and amide groups of protein in Pb(II) binding. Scanning electron microscopy (SEM) and fluorescence microscopy analysis displayed reduced growth of biofilm with altered surface topology in Pb(II) supplemented medium. Energy dispersive X-ray spectroscopy (EDX) analysis revealed the entrapment of Pb in the EPS. Uronic acid, a characteristic functional group of biofilm, was observed in 1H NMR spectroscopy. The findings suggest that biofilm associated EPS are perfect organic ligands for Pb(II) complexation and may significantly augment the bioavailability of Pb(II) in the metal contaminated environment for subsequent sequestration.

Switching from Controlled Ring-Opening Polymerization (cROP) to Controlled Ring-Closing Depolymerization (cRCDP) by Adjusting the Reaction Parameters That Determine the Ceiling Temperature

PubMed Central

2016-01-01

Full control over the ceiling temperature (Tc) enables a selective transition between the monomeric and polymeric state. This is exemplified by the conversion of the monomer 2-allyloxymethyl-2-ethyl-trimethylene carbonate (AOMEC) to poly(AOMEC) and back to AOMEC within 10 h by controlling the reaction from conditions that favor ring-opening polymerization (Tc > T0) (where T0 is the reaction temperature) to conditions that favor ring-closing depolymerization (Tc < T0). The ring-closing depolymerization (RCDP) mirrors the polymerization behavior with a clear relation between the monomer concentration and the molecular weight of the polymer, indicating that RCDP occurs at the chain end. The Tc of the polymerization system is highly dependent on the nature of the solvent, for example, in toluene, the Tc of AOMEC is 234 °C and in acetonitrile Tc = 142 °C at the same initial monomer concentration of 2 M. The control over the monomer to polymer equilibrium sets new standards for the selective degradation of polymers, the controlled release of active components, monomer synthesis and material recycling. In particular, the knowledge of the monomer to polymer equilibrium of polymers in solution under selected environmental conditions is of paramount importance for in vivo applications, where the polymer chain is subjected to both high dilution and a high polarity medium in the presence of catalysts, that is, very different conditions from which the polymer was formed. PMID:27783494

Iron-Based Redox Polymerization of Acrylic Acid for Direct Synthesis of Hydrogel/Membranes, and Metal Nanoparticles for Water Treatment

PubMed Central

Hernández, Sebastián; Papp, Joseph K.; Bhattacharyya, Dibakar

2014-01-01

Functionalized polymer materials with ion exchange groups and integration of nano-structured materials is an emerging area for catalytic and water pollution control applications. The polymerization of materials such as acrylic acid often requires persulfate initiator and a high temperature start. However, is generally known that metal ions accelerate such polymerizations starting from room temperature. If the metal is properly selected, it can be used in environmental applications adding two advantages simultaneously. This paper deals with this by polymerizing acrylic acid using iron as accelerant and its subsequent use for nanoparticle synthesis in hydrogel and PVDF membranes. Characterizations of hydrogel, membranes and nanoparticles were carried out with different techniques. Nanoparticles sizes of 30–60 nm were synthesized. Permeability and swelling measurements demonstrate an inverse relationship between hydrogel mesh size (6.30 to 8.34 nm) and membrane pores (222 to 110 nm). Quantitative reduction of trichloroethylene/chloride generation by Fe/Pd nanoparticles in hydrogel/membrane platforms was also performed. PMID:24954975

Iodine versus Bromine Functionalization for Bottom-Up Graphene Nanoribbon Growth: Role of Diffusion

DOE PAGES

Bronner, Christopher; Marangoni, Tomas; Rizzo, Daniel J.; ...

2017-08-08

Deterministic bottom-up approaches for synthesizing atomically well-defined graphene nanoribbons (GNRs) largely rely on the surface-catalyzed activation of selected labile bonds in a molecular precursor followed by step-growth polymerization and cyclodehydrogenation. While the majority of successful GNR precursors rely on the homolytic cleavage of thermally labile C–Br bonds, the introduction of weaker C–I bonds provides access to monomers that can be polymerized at significantly lower temperatures, thus helping to increase the flexibility of the GNR synthesis process. Scanning tunneling microscopy imaging of molecular precursors, activated intermediates, and polymers resulting from stepwise thermal annealing of both Br and I substituted precursors formore » chevron GNRs reveals that the polymerization of both precursors proceeds at similar temperatures on Au(111). Finally, this surprising observation is consistent with diffusion-controlled polymerization of the surface-stabilized radical intermediates that emerge from homolytic cleavage of either the C–Br or the C–I bonds.« less

The effects of light curing units and environmental temperatures on C 000000000000 000000000000 000000000000 111111111111 000000000000 111111111111 000000000000 000000000000 000000000000 C conversion of commercial and experimental bonding agents.

PubMed

Jafarzadeh-Kashi, Tahereh Sadat; Erfan, Mohmmad; Kalbasi, Salmeh; Ghadiri, Malihe; Rakhshan, Vahid

2014-10-01

Polymerization of bonding agents (BA) is a critical factor in determining the success of bonded restorations. We aimed to assess the effects of two light curing units and two temperatures on the extent of polymerization (EP) of a commercial BA and an experimental BA. Forty BA specimens were randomly divided into 8 subgroups of n = 5 to compare the polymerization of two BAs (experimental/Scotchbond) based on the variables: temperature (23/37 °C) and light-curing unit (quartz-tungsten-halogen/light-emitting diode). The EP (%) was measured using differential scanning calorimetry, and analyzed using the t-test, two- and three-way analyses of variance (ANOVA), and the Bonferroni test (α = 0.05). There were significant differences between the EP results between the two BAs (P = 0.012) and due to the different temperatures (P = 0.001), but not between the different light-curing units (P = 0.548). The interaction between BA and temperature was significant (P < 0.001). The other interactions were nonsignificant. The two light-curing units had similar effects on the EP. The EP values were better when curing was performed at human body temperature.

Crystal structure of an orthomyxovirus matrix protein reveals mechanisms for self-polymerization and membrane association.

PubMed

Zhang, Wenting; Zheng, Wenjie; Toh, Yukimatsu; Betancourt-Solis, Miguel A; Tu, Jiagang; Fan, Yanlin; Vakharia, Vikram N; Liu, Jun; McNew, James A; Jin, Meilin; Tao, Yizhi J

2017-08-08

Many enveloped viruses encode a matrix protein. In the influenza A virus, the matrix protein M1 polymerizes into a rigid protein layer underneath the viral envelope to help enforce the shape and structural integrity of intact viruses. The influenza virus M1 is also known to mediate virus budding as well as the nuclear export of the viral nucleocapsids and their subsequent packaging into nascent viral particles. Despite extensive studies on the influenza A virus M1 (FLUA-M1), only crystal structures of its N-terminal domain are available. Here we report the crystal structure of the full-length M1 from another orthomyxovirus that infects fish, the infectious salmon anemia virus (ISAV). The structure of ISAV-M1 assumes the shape of an elbow, with its N domain closely resembling that of the FLUA-M1. The C domain, which is connected to the N domain through a flexible linker, is made of four α-helices packed as a tight bundle. In the crystal, ISAV-M1 monomers form infinite 2D arrays with a network of interactions involving both the N and C domains. Results from liposome flotation assays indicated that ISAV-M1 binds membrane via electrostatic interactions that are primarily mediated by a positively charged surface loop from the N domain. Cryoelectron tomography reconstruction of intact ISA virions identified a matrix protein layer adjacent to the inner leaflet of the viral membrane. The physical dimensions of the virion-associated matrix layer are consistent with the 2D ISAV-M1 crystal lattice, suggesting that the crystal lattice is a valid model for studying M1-M1, M1-membrane, and M1-RNP interactions in the virion.

Molecularly Oriented Polymeric Thin Films for Space Applications

NASA Technical Reports Server (NTRS)

Fay, Catharine C.; Stoakley, Diane M.; St.Clair, Anne K.

1997-01-01

The increased commitment from NASA and private industry to the exploration of outer space and the use of orbital instrumentation to monitor the earth has focused attention on organic polymeric materials for a variety of applications in space. Some polymeric materials have exhibited short-term (3-5 yr) space environmental durability; however, future spacecraft are being designed with lifetimes projected to be 10-30 years. This gives rise to concern that material property change brought about during operation may result in unpredicted spacecraft performance. Because of their inherent toughness and flexibility, low density, thermal stability, radiation resistance and mechanical strength, aromatic polyimides have excellent potential use as advanced materials on large space structures. Also, there exists a need for high temperature (200-300 C) stable, flexible polymeric films that have high optical transparency in the 300-600nm range of the electromagnetic spectrum. Polymers suitable for these space applications were fabricated and characterized. Additionally, these polymers were molecularly oriented to further enhance their dimensional stability, stiffness, elongation and strength. Both unoriented and oriented polymeric thin films were also cryogenically treated to temperatures below -184 C to show their stability in cold environments and determine any changes in material properties.

Selective sorption of lead, cadmium and zinc ions by a polymeric cation exchanger containing nano-Zr(HPO3S)2.

PubMed

Zhang, Qingrui; Pan, Bingcai; Pan, Bingjun; Zhang, Weiming; Jia, Kun; Zhang, Quanxing

2008-06-01

A novel polymeric hybrid sorbent, namely ZrPS-001, was fabricated for enhanced sorption of heavy metal ions by impregnating Zr(HPO3S)2 (i.e., ZrPS) nanoparticles within a porous polymeric cation exchanger D-001. The immobilized negatively charged groups bound to the polymeric matrix D-001 would result in preconcentration and permeation enhancement of target metal ions prior to sequestration, and ZrPS nanoparticles are expected to sequester heavy metals selectively through an ion-exchange process. Highly effective sequestration of lead, cadmium, and zinc ions from aqueous solution can be achieved by ZrPS-001 even in the presence of competing calcium ion at concentration several orders of magnitude greater than the target species. The exhausted ZrPS-001 beads are amenable to regeneration with 6 M HCI solution for repeated use without any significant capacity loss. Fixed-bed column treatment of simulated waters containing heavy metals at high or trace levels was also performed. The content of heavy metals in treated effluent approached or met the WHO drinking water standard.

Direct laser writing of synthetic poly(amino acid) hydrogels and poly(ethylene glycol) diacrylates by two-photon polymerization.

PubMed

Käpylä, Elli; Sedlačík, Tomáš; Aydogan, Dogu Baran; Viitanen, Jouko; Rypáček, František; Kellomäki, Minna

2014-10-01

The additive manufacturing technique of direct laser writing by two-photon polymerization (2PP-DLW) enables the fabrication of three-dimensional microstructures with superior accuracy and flexibility. When combined with biomimetic hydrogel materials, 2PP-DLW can be used to recreate the microarchitectures of the extracellular matrix. However, there are currently only a limited number of hydrogels applicable for 2PP-DLW. In order to widen the selection of synthetic biodegradable hydrogels, in this work we studied the 2PP-DLW of methacryloylated and acryloylated poly(α-amino acid)s (poly(AA)s). The performance of these materials was compared to widely used poly(ethylene glycol) diacrylates (PEGdas) in terms of polymerization and damage thresholds, voxel size, line width, post-polymerization swelling and deformation. We found that both methacryloylated and acryloylated poly(AA) hydrogels are suitable to 2PP-DLW with a wider processing window than PEGdas. The poly(AA) with the highest degree of acryloylation showed the greatest potential for 3D microfabrication. Copyright © 2014 Elsevier B.V. All rights reserved.

Microfluidic-Assisted Production of Size-Controlled Superparamagnetic Iron Oxide Nanoparticles-Loaded Poly(methyl methacrylate) Nanohybrids.

PubMed

Ding, Shukai; Attia, Mohamed F; Wallyn, Justine; Taddei, Chiara; Serra, Christophe A; Anton, Nicolas; Kassem, Mohamad; Schmutz, Marc; Er-Rafik, Meriem; Messaddeq, Nadia; Collard, Alexandre; Yu, Wei; Giordano, Michele; Vandamme, Thierry F

2018-02-06

In this paper, superparamagnetic iron oxide nanoparticles (SPIONs, around 6 nm) encapsulated in poly(methyl methacrylate) nanoparticles (PMMA NPs) with controlled sizes ranging from 100 to 200 nm have been successfully produced. The hybrid polymeric NPs were prepared following two different methods: (1) nanoprecipitation and (2) nanoemulsification-evaporation. These two methods were implemented in two different microprocesses based on the use of an impact jet micromixer and an elongational-flow microemulsifier. SPIONs-loaded PMMA NPs synthesized by the two methods presented completely different physicochemical properties. The polymeric NPs prepared with the micromixer-assisted nanoprecipitation method showed a heterogeneous dispersion of SPIONs inside the polymer matrix, an encapsulation efficiency close to 100 wt %, and an irregular shape. In contrast, the polymeric NPs prepared with the microfluidic-assisted nanoemulsification-evaporation method showed a homogeneous dispersion, an almost complete encapsulation, and a spherical shape. The properties of the polymeric NPs have been characterized by dynamic light scattering, thermogravimetric analysis, and transmission electron microscope. In vitro cytotoxicity assays were also performed on the nanohybrids and pure PMMA NPs.

The application of novel nano-thermal and imaging techniques for monitoring drug microstructure and distribution within PLGA microspheres.

PubMed

Yang, Fan; Chen, De; Guo, Zhe-Fei; Zhang, Yong-Ming; Liu, Yi; Askin, Sean; Craig, Duncan Q M; Zhao, Min

2017-04-30

Poly (d,l-lactic-co-glycolic) acid (PLGA) based microspheres have been extensively used as controlled drug release systems. However, the burst effect has been a persistent issue associated with such systems, especially for those prepared by the double emulsion technique. An effective approach to preventing the burst effect and achieving a more ideal drug release profile is to improve the drug distribution within the polymeric matrix. Therefore, it is of great importance to establish a rapid and robust tool for screening and optimizing the drug distribution during pre-formulation. Transition Temperature Microscopy (TTM), a novel nano-thermal and imaging technique, is an extension of nano-thermal analysis (nano-TA) whereby a transition temperature is detected at a localized region of a sample and then designated a color based on a particular temperature/color palette, finally resulting in a coded map based on transition temperatures detected by carrying out a series of nanoTA measurements across the surface of the sample. In this study, we investigate the feasibility of applying the aforementioned technique combined with other thermal, imaging and structural techniques for monitoring the drug microstructure and spatial distribution within bovine serum albumin (BSA) loaded and nimodipine loaded PLGA microspheres, with a view to better predicting the in vitro drug release performance. Copyright © 2017 Elsevier B.V. All rights reserved.

Injectable Ceramic Microcast Silicon Carbonitride (SiCN) Microelectromechanical System (MEMS) for Extreme Temperature Environments with Extension: Micro Packages for Nano-Devices

DTIC Science & Technology

2004-01-01

pyrolyzed to produce the ceramic (SiCN) parts, or they may be retained in the polymeric state and used as high-temperature polymer /glass MEMS devices. Two...structure and the SU8 /wafer is weak due to the Teflon coating. (j) A free standing polymer structure results. The structure is then crosslinked and... polymer . Further efforts are necessary to identify the least damaging rinsing chemicals, that is, chemicals which would not contaminate polymerized

Adenosine Monophosphate Forms Ordered Arrays in Multilamellar Lipid Matrices: Insights into Assembly of Nucleic Acid for Primitive Life

PubMed Central

Toppozini, Laura; Dies, Hannah; Deamer, David W.; Rheinstädter, Maikel C.

2013-01-01

A fundamental question of biology is how nucleic acids first assembled and then were incorporated into the earliest forms of cellular life 4 billion years ago. The polymerization of nucleotides is a condensation reaction in which phosphodiester bonds are formed. This reaction cannot occur in aqueous solutions, but guided polymerization in an anhydrous lipid environment could promote a non-enzymatic condensation reaction in which oligomers of single stranded nucleic acids are synthesized. We used X-ray scattering to investigate 5′-adenosine monophosphate (AMP) molecules captured in a multilamellar phospholipid matrix composed of dimyristoylphosphatidylcholine. Bragg peaks corresponding to the lateral organization of the confined AMP molecules were observed. Instead of forming a random array, the AMP molecules are highly entangled, with the phosphate and ribose groups in close proximity. This structure may facilitate polymerization of the nucleotides into RNA-like polymers. PMID:23667523

Adenosine monophosphate forms ordered arrays in multilamellar lipid matrices: insights into assembly of nucleic acid for primitive life.

PubMed

Toppozini, Laura; Dies, Hannah; Deamer, David W; Rheinstädter, Maikel C

2013-01-01

A fundamental question of biology is how nucleic acids first assembled and then were incorporated into the earliest forms of cellular life 4 billion years ago. The polymerization of nucleotides is a condensation reaction in which phosphodiester bonds are formed. This reaction cannot occur in aqueous solutions, but guided polymerization in an anhydrous lipid environment could promote a non-enzymatic condensation reaction in which oligomers of single stranded nucleic acids are synthesized. We used X-ray scattering to investigate 5'-adenosine monophosphate (AMP) molecules captured in a multilamellar phospholipid matrix composed of dimyristoylphosphatidylcholine. Bragg peaks corresponding to the lateral organization of the confined AMP molecules were observed. Instead of forming a random array, the AMP molecules are highly entangled, with the phosphate and ribose groups in close proximity. This structure may facilitate polymerization of the nucleotides into RNA-like polymers.

The Effect of Microporous Polymeric Support Modification on Surface and Gas Transport Properties of Supported Ionic Liquid Membranes

PubMed Central

Akhmetshina, Alsu A.; Davletbaeva, Ilsiya M.; Grebenschikova, Ekaterina S.; Sazanova, Tatyana S.; Petukhov, Anton N.; Atlaskin, Artem A.; Razov, Evgeny N.; Zaripov, Ilnaz I.; Martins, Carla F.; Neves, Luísa A.; Vorotyntsev, Ilya V.

2015-01-01

Microporous polymers based on anionic macroinitiator and toluene 2,4-diisocyanate were used as a support for 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim][Tf2N]) immobilization. The polymeric support was modified by using silica particles associated in oligomeric media, and the influence of the modifier used on the polymeric structure was studied. The supported ionic liquid membranes (SILMs) were tested for He, N2, NH3, H2S, and CO2 gas separation and ideal selectivities were calculated. The high values of ideal selectivity for ammonia-based systems with permanent gases were observed on polymer matrixes immobilized with [bmim][PF6] and [emim][Tf2N]. The modification of SILMs by nanosize silica particles leads to an increase of NH3 separation relatively to CO2 or H2S. PMID:26729177

The characterization of high-density polyethylene/organoclay nanocomposites

NASA Astrophysics Data System (ADS)

Rodrigues, Tathiane Cordeiro; Tavares, Maria Inês Bruno; Soares, Igor Lopes; Moreira, Ana M.

2009-01-01

Polymeric nanocomposites, which are hybrids of polymers and modified inorganic clay with organic surfactants, are extremely attractive in both science and industry. These materials present improvements in such polymer properties as modulus, heat capacity, thermal stability, flame resistance, and so on. Research has been conducted in recent decades to obtain high-quality materials that can be used in applications like food packing, car components, and combustible cells. Polymeric nanocomposites present many advantages in relation to composites due to the quantity of filler added to the polymer and also to the improved properties. In a composite, the quantity of filler must be as high as possible (i.e., over 30%). In the polymeric nanocomposite the quantity of filler varies from 1% to 5% because of the nanosize of the particles. These nanoparticles often have a large surface area that results in improved polymer-matrix properties.

Hydrogel nanoparticle based immunoassay

DOEpatents

Liotta, Lance A; Luchini, Alessandra; Petricoin, Emanuel F; Espina, Virginia

2015-04-21

An immunoassay device incorporating porous polymeric capture nanoparticles within either the sample collection vessel or pre-impregnated into a porous substratum within fluid flow path of the analytical device is presented. This incorporation of capture particles within the immunoassay device improves sensitivity while removing the requirement for pre-processing of samples prior to loading the immunoassay device. A preferred embodiment is coreshell bait containing capture nanoparticles which perform three functions in one step, in solution: a) molecular size sieving, b) target analyte sequestration and concentration, and c) protection from degradation. The polymeric matrix of the capture particles may be made of co-polymeric materials having a structural monomer and an affinity monomer, the affinity monomer having properties that attract the analyte to the capture particle. This device is useful for point of care diagnostic assays for biomedical applications and as field deployable assays for environmental, pathogen and chemical or biological threat identification.

Effect of cellulose nanowhiskers functionalization with polyaniline for epoxy coatings

NASA Astrophysics Data System (ADS)

Borsoi, C.; Zattera, A. J.; Ferreira, C. A.

2016-02-01

Functionalization of cellulose nanowhiskers (CNW) was performed by means of chemical synthesis involving polymerization of polyaniline in emeraldine salt form (PAni SE) in the presence of CNW. Thermal, chemical and morphological samples properties were evaluated. Polymeric coatings were obtained with epoxy, aminopropyltriethoxysilane (APS), CNW and CNW/PAni SE applied on carbon steel with a conversion coating of zirconia (Zr) and the mechanical properties were evaluated. With regard to CNW functionalization the sample was encapsulated with PAni SE as observed by FTIR and morphologic analysis, with decreased thermal stability. Regarding the mechanical properties of CNW and CNW/PAni SE polymeric coatings, improvements in flexibility and hardness properties using the APS and Zr layer were observed. The adherence of polymer coatings improved by the incorporation of CNW and CNW/PAni SE. Through morphological analysis it was observed that CNW shows good dispersion in the polymer matrix without agglomerates formation.

Dispersion Polymerization of Polystyrene Particles Using Alcohol as Reaction Medium

NASA Astrophysics Data System (ADS)

Cho, Young-Sang; Shin, Cheol Hwan; Han, Sujin

2016-02-01

In this study, monodisperse polystyrene nanospheres were prepared by dispersion polymerization using alcohol as reaction medium to prepare colloidal clusters of the latex beads. Polyvinylpyrrolidone (PVP) and 2-(methacryloyloxy)ethyltrimethylammonium chloride (MTC) were used as dispersion stabilizer and comonomer, respectively. The particle size could be controlled by adjusting the reactant compositions such as the amount of stabilizer, comonomer, and water in the reactant mixture. The size and monodispersity of the polymeric particles could be also controlled by changing the reaction medium with different alcohols other than ethanol or adjusting the polymerization temperature. The synthesized particles could be self-organized inside water-in-oil emulsion droplets by evaporation-driven self-assembly to produce colloidal clusters of the polymeric nanospheres.

Modification of conductive polyaniline with carbon nanomaterials

NASA Astrophysics Data System (ADS)

Sedaghat, Sajjad; Alavijeh, Mahdi Soleimani

2014-08-01

The synthesis of polyaniline/single-wall nanotube, polyaniline/multi-wall nanotube and polyaniline/single-wall nanotube/graphen nanosheets nanocomposites by in situ polymerization are reported in this study. The substrates were treated with a mixture of concentrated sulfuric acid and concentrated nitric acid before usage to functionalize with carboxylic and hydroxyl groups. Aniline monomers are adsorbed and polymerized on the surface of these fillers. Structural analysis using scanning electron microscopy showed that nanomaterials dispersed into polymer matrix and made tubular structures with diameters several tens to hundreds nanometers depending on the polyaniline content. These nanocomposites can be used for production of excellent electrode materials applications in high-performance supercapacitors.

Highly ordered nanocomposites via a monomer self-assembly in situ condensation approach

DOEpatents

Gin, D.L.; Fischer, W.M.; Gray, D.H.; Smith, R.C.

1998-12-15

A method for synthesizing composites with architectural control on the nanometer scale is described. A polymerizable lyotropic liquid-crystalline monomer is used to form an inverse hexagonal phase in the presence of a second polymer precursor solution. The monomer system acts as an organic template, providing the underlying matrix and order of the composite system. Polymerization of the template in the presence of an optional cross-linking agent with retention of the liquid-crystalline order is carried out followed by a second polymerization of the second polymer precursor within the channels of the polymer template to provide an ordered nanocomposite material. 13 figs.

Proton-transfer lasers based on solid copolymers of modified 2-(2'-hydroxyphenyl)benzimidazoles with methacrylate monomers

NASA Astrophysics Data System (ADS)

Costela, A.; García-Moreno, I.; Mallavia, Ricardo; Amat-Guerri, F.; Barroso, J.; Sastre, R.

1998-06-01

We report on the lasing action of two newly synthesized 2-(2'-hydroxyphenyl) benzimidazole derivatives copolymerized with methyl methacrylate. The laser samples were transversely pumped with a N 2 laser at 337 nm. The influence on the proton-transfer laser performance of the distance between the chromophore group and the polymeric main chain and of the rigidity of the polymeric host matrix, were studied. Significant increases in lasing efficiency and photostability are demonstrated for some of the new materials, as compared to those previously obtained with related proton-transfer dyes also covalently bound to methacrylic monomers.

Highly ordered nanocomposites via a monomer self-assembly in situ condensation approach

DOEpatents

Gin, Douglas L.; Fischer, Walter M.; Gray, David H.; Smith, Ryan C.

1998-01-01

A method for synthesizing composites with architectural control on the nanometer scale is described. A polymerizable lyotropic liquid-crystalline monomer is used to form an inverse hexagonal phase in the presence of a second polymer precursor solution. The monomer system acts as an organic template, providing the underlying matrix and order of the composite system. Polymerization of the template in the presence of an optional cross-linking agent with retention of the liquid-crystalline order is carried out followed by a second polymerization of the second polymer precursor within the channels of the polymer template to provide an ordered nanocomposite material.

HDPE-HA composites synthetized by in situ polymerization with different filler content

NASA Astrophysics Data System (ADS)

Hermán, V.; Karam, A.; Albano, C.; Romero, K.; González, G.

2012-07-01

In Situ ethylene polymerization was used to synthesize high density polyethylene - hydroxyapatite (HDPE-HA) composites, employing Cp2ZrCl2/MAO as catalytic system. A good dispersion of HA into the HDPE matrix was obtained when the following synthesis conditions were combined: high stirring velocities (2000 rpm), low quantities of solvent (100 mL), and 10 °C. Under these conditions different filler content was used to synthetized HDPE-HA composites. An interaction between HA and HDPE was obtained by FTIR. On the other hand, thermal analysis indicated that no significant differences were observed between HDPE and the composites.

Polymerization of amino acids under high-pressure conditions: Implication to chemical evolution on the early Earth

NASA Astrophysics Data System (ADS)

Kakegawa, T.; Ohara, S.; Ishiguro, T.; Abiko, H.; Nakazawa, H.

2008-12-01

Prebiotic polymerization of amino acids is the most fundamental reaction to promote the chemical evolution for origin of life. Polymerization of amino acids is the dehydration reaction. This questions as to if submarine hydrothermal conditions, thus hydrated enironments, were appropreate for peptide formations. Our previous experiments implied that non-aqueous and high-pressure environments (more than 20 MPa) would be suitable for polymerization of amino acids (Ohara et al., 2006). This leads to the hypothesis that the first peptides may have formed in the Hadean oceanic crustal environments, where dehydration proceeded with availability of appropriate temperatures and pressures. In the present study, experiments simulating the crustal conditions were performed with various pressures (1-175 MPa) and temperatures (100- 200 C degree) using autoclaves. Purified powders (100 mg) of alanine, glycine, valine and aspartic acid were used in the experiments without mixing water in order to examine the solid-solid reactions. The products were analyzed using HPLC and LC-MS. Results indicate that: (1) longer time is required to form peptide compared to those of previous aqueous experiments; (2) pressure has a role to limit the production of melanoidine and cyclic amino acids, which are inhibitors for elongation of peptides; (3) glycine was polymerized up to 11-mer, which was not formed in any previous experiments without catalyses; (4) valine was polymerized up to 3-mer; and (5) aspartic acid was polymerized to 4-mer, accompanied with production of other amino acids. It is noteworthy that high-pressure environments favor all examined polymerization reactions. Such situations would have happened inside of deep oceanic crusts of the early Earth.

Cryomilling for the fabrication of doxorubicin-containing silica-nanoparticle/polycaprolactone nanocomposite films

NASA Astrophysics Data System (ADS)

Gao, Yu; Lim, Jing; Han, Yiyuan; Wang, Lifeng; Chong, Mark Seow Khoon; Teoh, Swee-Hin; Xu, Chenjie

2016-01-01

Bionanocomposites need to have a homogeneous distribution of nanomaterials in the polymeric matrix to achieve consistent mechanical and biological functions. However, a significant challenge lies in achieving the homogeneous distribution of nanomaterials, particularly through a solvent-free approach. This report introduces a technology to address this need. Specifically, cryomilling, a solvent-free, low-temperature processing method, was applied to generate a bionanocomposite film with well-dispersed nanoparticles. As a proof-of-concept, polycaprolactone (PCL) and doxorubicin-containing silica nanoparticles (Si-Dox) were processed through cryomilling and subsequently heat pressed to form the PCL/Si-Dox (cPCL/Si-Dox) film. Homogeneous distribution of Si-Dox was observed under both confocal imaging and atomic force microscopy imaging. The mechanical properties of cPCL/Si-Dox were comparable to those of the pure PCL film. Subsequent in vitro release profiles suggested that sustained release of Dox from the cPCL/Si-Dox film was achievable over 50 days. When human cervical cancer cells were seeded directly on these films, uptake of Dox was observed as early as day 1 and significant inhibition of cell growth was recorded on day 5.Bionanocomposites need to have a homogeneous distribution of nanomaterials in the polymeric matrix to achieve consistent mechanical and biological functions. However, a significant challenge lies in achieving the homogeneous distribution of nanomaterials, particularly through a solvent-free approach. This report introduces a technology to address this need. Specifically, cryomilling, a solvent-free, low-temperature processing method, was applied to generate a bionanocomposite film with well-dispersed nanoparticles. As a proof-of-concept, polycaprolactone (PCL) and doxorubicin-containing silica nanoparticles (Si-Dox) were processed through cryomilling and subsequently heat pressed to form the PCL/Si-Dox (cPCL/Si-Dox) film. Homogeneous distribution of Si-Dox was observed under both confocal imaging and atomic force microscopy imaging. The mechanical properties of cPCL/Si-Dox were comparable to those of the pure PCL film. Subsequent in vitro release profiles suggested that sustained release of Dox from the cPCL/Si-Dox film was achievable over 50 days. When human cervical cancer cells were seeded directly on these films, uptake of Dox was observed as early as day 1 and significant inhibition of cell growth was recorded on day 5. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07287e

Performance Enhancement Using Selective Reinforcement for Metallic Single- and Multi-Pin Loaded Holes

NASA Technical Reports Server (NTRS)

Farley, Gary L.; Seshadri, Banavara R.

2005-01-01

An analysis based investigation of aluminum with metal matrix composite selectively reinforced single- and multi-hole specimens was performed and their results compared with results from geometrically comparable non-reinforced specimens. All reinforced specimens exhibited a significant increase in performance. Performance increase of up to 170 percent was achieved. Specimen failure modes were consistent with results from reinforced polymeric matrix composite specimens. Localized reinforcement application (circular) proved as effective as a broader area (strip) reinforcement. Also, selective reinforcement is an excellent method of increasing the performance of multi-hole specimens.

Induction Curing of Thiol-acrylate and Thiolene Composite Systems

PubMed Central

Ye, Sheng; Cramer, Neil B.; Stevens, Blake E.; Sani, Robert L.; Bowman, Christopher N.

2011-01-01

Induction curing is demonstrated as a novel type of in situ radiation curing that maintains most of the advantages of photocuring while eliminating the restriction of light accessibility. Induction curing is utilized to polymerize opaque composites comprised of thiol-acrylate and thiol-ene resins, nanoscale magnetic particles, and carbon nanotubes. Nanoscale magnetic particles are dispersed in the resin and upon exposure to the magnetic field, these particles lead to induction heating that rapidly initiates the polymerization. Heat transfer profiles and reaction kinetics of the samples are modeled during the reactions with varying induction heater power, species concentration, species type and sample thickness, and the model is compared with the experimental results. Thiol-ene polymerizations achieved full conversion between 1.5 minutes and 1 hour, depending on the field intensity and the composition, with the maximum reaction temperature decreasing from 146 – 87 °C when the induction heater power was decreased from 8 – 3 kW. The polymerization reactions of the thiol-acrylate system were demonstrated to achieve full conversion between 0.6 and 30 minutes with maximum temperatures from 139 to 86 °C. The experimental behavior was characterized and the temperature profile modeled for the thiol-acrylate composite comprised of sub100nm nickel particles and induction heater power in the range of 32 to 20 kW. A 9°C average deviation was observed between the modeling and experimental results for the maximum temperature rise. The model also was utilized to predict reaction temperatures and kinetics for systems with varying thermal initiator concentration, initiator half-life, monomer molecular weight and temperature gradients in samples with varying thickness, thereby demonstrating that induction curing represents a designable and tunable polymerization method. Finally, induction curing was utilized to cure thiol-acrylate systems containing carbon nanotubes where 1 wt% carbon nanotubes resulted in systems where the storage modulus increased from 17.6 ± 0.2 to 21.6 ± 0.1 MPa and an electrical conductivity that increased from <10−7 to 0.33 ± 0.5 S/m. PMID:21765552

Bioactive Polymeric Materials for Tissue Repair

PubMed Central

Bienek, Diane R.; Tutak, Wojtek; Skrtic, Drago

2017-01-01

Bioactive polymeric materials based on calcium phosphates have tremendous appeal for hard tissue repair because of their well-documented biocompatibility. Amorphous calcium phosphate (ACP)-based ones additionally protect against unwanted demineralization and actively support regeneration of hard tissue minerals. Our group has been investigating the structure/composition/property relationships of ACP polymeric composites for the last two decades. Here, we present ACP’s dispersion in a polymer matrix and the fine-tuning of the resin affects the physicochemical, mechanical, and biological properties of ACP polymeric composites. These studies illustrate how the filler/resin interface and monomer/polymer molecular structure affect the material’s critical properties, such as ion release and mechanical strength. We also present evidence of the remineralization efficacy of ACP composites when exposed to accelerated acidic challenges representative of oral environment conditions. The utility of ACP has recently been extended to include airbrushing as a platform technology for fabrication of nanofiber scaffolds. These studies, focused on assessing the feasibility of incorporating ACP into various polymer fibers, also included the release kinetics of bioactive calcium and phosphate ions from nanofibers and evaluate the biorelevance of the polymeric ACP fiber networks. We also discuss the potential for future integration of the existing ACP scaffolds into therapeutic delivery systems used in the precision medicine field. PMID:28134776

Investigation of dielectric properties of polymer composites reinforced with carbon nanotubes in the frequency band of 0.01 Hz - 10 MHz

NASA Astrophysics Data System (ADS)

Goshev, A. A.; Eseev, M. K.; Kapustin, S. N.; Vinnik, L. N.; Volkov, A. S.

2016-08-01

The goal of this work is experimental study of dielectric properties of polymer nanocomposites reinforced with multiwalled carbon nanotubes (MWCNTs) in alternating electric field in low frequency band of 0.01 Hz - 10 MHz. We investigated the influence, functionalization degree, aspect ratio, concentration of carbon nanotubes (CNTs) on dielectric properties of polymer sample. We also studied the dependence of dielectric properties on the polymerization temperature. The dependence of CNTs agglomeration on sample polymerization temperature and temperature's influence on conductivity has been shown. We conducted model calculation of percolation threshold and figured out its dependence on CNTs aspect ratio.

Effet des Plastifiants sur la Temperature de Transition Vitreuse, Tg, du Butadiene a Terminaison Hydroxy et du Polyazoture de Glycidyle - Simulations et Experiences (Effect of the Plasticizers on the Vitreous Transition Temperature, Tg, of the Butadiene to Termination Hydroxy and the Polyazoture of Glycidyle - Simulations and Experiences)

DTIC Science & Technology

2008-09-01

diverses temperatures 26 a) HTPB pur b) HTPB-DOA (polymere et plastifiant) c) GAP pur d) Gpl pur e)Gap-Gpl Liste des tableaux Tableau 1...Composition des mailles amorphes construites 11 Tableau 2. Proprietes des polymeres et plastifiants utilises 11 Tableau 3. Comparaisons entre les Tt...obtenues experimentalement, les T% publiees dans les ecrits scientifiques et celles predites a partir des 7"gdes composes purs 19 Tableau 4. Comparaison

Effect of initiators on synthesis of poly(L-lactide) by ring opening polymerization

NASA Astrophysics Data System (ADS)

Pholharn, D.; Srithep, Y.; Morris, J.

2017-06-01

We studied the effect of several aliphatic alcohols, including1-dodecanol, 1-octanol and methanol, as initiators on synthesis of poly(L-lactide) (PLLA) by ring opening polymerization. The reaction starts with L-lactide monomer and uses stannous octoate as catalyst. Fourier transform infrared spectroscopy and X-ray diffraction analysis verified that PLLAs were produced successfully. Weight, number average molecular weight and polydispersity index of PLLAs were measured by gel permeation chromatography. The PLLA initiated by methanol (PLLA-Meth) presented the highest molecular weight and yield percent. From differential scanning calorimetry, PLLA-Meth showed the highest melting temperature at ∼167°C, crystallization temperature at 110°C and degree of crystallinity 80%. The thermal stability was assessed by thermogravimetric analysis: this confirmed that PLLA-Meth was superior with the highest degradation temperature compared to PLLA initiated by other initiators. We concluded that methanol was the most appropriate initiator for PLLA synthesis by ring opening polymerization.

Effect of flaw size and temperature on the matrix cracking behavior of a brittle ceramic matrix composite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anandakumar, U.; Webb, J.E.; Singh, R.N.

The matrix cracking behavior of a zircon matrix - uniaxial SCS 6 fiber composite was studied as a function of initial flaw size and temperature. The composites were fabricated by a tape casting and hot pressing technique. Surface flaws of controlled size were introduced using a vicker`s indenter. The composite samples were tested in three point flexure at three different temperatures to study the non steady state and steady state matrix cracking behavior. The composite samples exhibited steady state and non steady matrix cracking behavior at all temperatures. The steady state matrix cracking stress and steady state crack size increasedmore » with increasing temperature. The results of the study correlated well with the results predicted by the matrix cracking models.« less

Effect of Temperature Variations on Molecular Weight Distributions - Batch, Chain Addition Polymerizations

DTIC Science & Technology

those that might be formed by temperature variations in real reactors. Under most conditions, temperature variations appear to have a much greater effect on MWD than residence time distributions and micromixing .

Sulfonated poly(ether ether ketone)/polypyrrole core-shell nanofibers: a novel polymeric adsorbent/conducting polymer nanostructures for ultrasensitive gas sensors.

PubMed

Wang, Wei; Li, Zhenyu; Jiang, Tingting; Zhao, Zhiwei; Li, Ye; Wang, Zhaojie; Wang, Ce

2012-11-01

Conducting polymers-based gas sensors have attracted increasing research attention these years. The introduction of inorganic sensitizers (noble metals or inorganic semiconductors) within the conducting polymers-based gas sensors has been regarded as the generally effective route for further enhanced sensors. Here we demonstrate a novel route for highly-efficient conducting polymers-based gas sensors by introduction of polymeric sensitizers (polymeric adsorbent) within the conducting polymeric nanostructures to form one-dimensional polymeric adsorbent/conducting polymer core-shell nanocomposites, via electrospinning and solution-phase polymerization. The adsorption effect of the SPEEK toward NH₃ can facilitate the mass diffusion of NH₃ through the PPy layers, resulting in the enhanced sensing signals. On the basis of the SPEEK/PPy nanofibers, the sensors exhibit large gas responses, even when exposed to very low concentration of NH₃ (20 ppb) at room temperature.

A new method for the preparation of polymeric porous layer open tubular columns for GC application

NASA Technical Reports Server (NTRS)

Shen, T. C.; Wang, M. L.

1995-01-01

A new method to prepare polymeric PLOT columns by using in situ polymerization technology is described. The method involves a straightforward in situ polymerization of the monomer. The polymer produced is directly coated on the metal tubing. This eliminates many of the steps needed in conventional polymeric PLOT column preparation. Our method is easy to operate and produces very reproducible columns, as shown previously (T. C. Shen. J. Chromatogr. Sci. 30, 239, 1992). The effects of solvents, tubing pretreatments, initiators and reaction temperatures in the preparation of PLOT columns are studied. Several columns have been developed to separate (1) highly polar compounds, such as water and ammonia or water and HCN, and (2) hydrocarbons and inert gases. A recent improvement has allowed us to produce bonded polymeric PLOT columns. These were studied, and the results are included also.

Method of chemical vapor deposition of boron nitride using polymeric cyanoborane

DOEpatents

Maya, Leon

1994-01-01

Polymeric cyanoborane is volatilized, decomposed by thermal or microwave plasma energy, and deposited on a substrate as an amorphous film containing boron, nitrogen and carbon. Residual carbon present in the film is removed by ammonia treatment at an increased temperature, producing an adherent, essentially stoichiometric boron nitride film.