Alternative Fluoropolymers to Avoid the Challenges Associated with Perfluorooctanoic Acid

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

Guo,J.; Resnick, P.; Efimenko, K.

2008-01-01

The degradation of stain-resistant coating materials leads to the release of biopersistent perfluorooctanoic acid (PFOA) to the environment. In order to find the environmentally friendly substitutes, we have designed and synthesized a series of nonbiopersistant fluorinated polymers containing perfluorobutyl groups in the side chains. The surface properties of the new coating materials were characterized by static and dynamic contact angle measurements. The new coating materials demonstrate promising hydrophobic and oleophobic properties with low surfaces tensions. The wetting properties and surface structure of the polymers were tuned by varying the 'spacer' structures between the polymer backbones and the perfluorinated groups ofmore » the side chains. The relationship between orientations of the fluorinated side chains and performances of polymer surfaces were further investigated by near-edge X-ray fine absorption structure (NEXAFS) experiments and differential scanning calorimetry (DSC).« less

Optical monitoring of proteins at solid interfaces

NASA Astrophysics Data System (ADS)

Dunne, G.; McDonnell, L.; Miller, R.; McMillan, N. D.; O'Rourke, B.; Mitchell, C. I.

2005-06-01

The adsorption properties of polymers are of great importance for implant studies. A better understanding of these properties can lead to improved implant materials. In this study the surface energy of different polymers was derived from contact angle measurements taken using profile analysis tensiometry (PAT) of sessile drops of water. The contact angles were measured for advancing and receding water drops on polished polymer surfaces and also on polymer surfaces modified by adsorbing protein to the surface prior to analysis of the sessile drop. The protein used was bovine serum albumin (BSA) and the surfaces were poly-methylmethacrylate (PMMA), poly-ether-ether-ketone (PEEK) and stainless steel. The polymer surfaces were also studied using atomic force microscopy (AFM). Images of the surfaces were taken in different states: rough, smooth and with albumin adsorbed. As a method to identify the proteins on the surface easier, anti-albumin antibodies with 30nm nano gold particles attached were adsorbed to the albumin on the surfaces. Using nano gold particles made the imaging more straightforward and thus made identification of the protein on the surface easier. The results from this work show the differing hydrophobicities of polymer surfaces under different conditions and a new nanotechnological method of protein identification.

Molecular dynamics study of binding energies, mechanical properties, and detonation performances of bicyclo-HMX-based PBXs.

PubMed

Qiu, Ling; Xiao, Heming

2009-05-15

To investigate the effect of polymer binders on the monoexplosive, molecular dynamics simulations were performed to study the binding energies, mechanical properties, and detonation performances of the bicyclo-HMX-based polymer-bonded explosives (PBXs). The results show that the binding energies on different crystalline surfaces of bicyclo-HMX decrease in the order of (010)>(100)>(001). On each crystalline surface, binding properties of different polymers with the same chain segment are different from each other, while those of the polymers in the same content decrease in the sequence of PVDF>F(2311)>F(2314) approximately PCTFE. The mechanical properties of a dozen of model systems (elastic coefficients, various moduli, Cauchy pressure, and Poisson's ratio) have been obtained. It is found that mechanical properties are effectively improved by adding small amounts of fluorine polymers, and the overall effect of fluorine polymers on three crystalline surfaces of bicyclo-HMX changes in the order of (010)>(001) approximately (100). In comparison with the base explosive, detonation performances of the PBXs decrease slightly, but they are still superior to TNT. These suggestions may be useful for the formulation design of bicyclo-HMX-based PBXs.

The wettability and swelling of selected mucoadhesive polymers in simulated saliva and vaginal fluids.

PubMed

Rojewska, M; Olejniczak-Rabinek, M; Bartkowiak, A; Snela, A; Prochaska, K; Lulek, J

2017-08-01

The surface properties play a particularly important role in the mucoadhesive drug delivery systems. In these formulations, the adsorption of polymer matrix to mucous membrane is limited by the wetting and swelling process of the polymer structure. Hence, the performance of mucoadhesive drug delivery systems made of polymeric materials depends on multiple factors, such as contact angle, surface free energy and water absorption rate. The aim of our study was to analyze the effect of model saliva and vaginal fluids on the wetting properties of selected mucoadhesive (Carbopol 974P NF, Noveon AA-1, HEC) and film-forming (Kollidon VA 64) polymers as well as their blends at the weight ratio 1:1 and 1:1:1, prepared in the form of discs. Surface properties of the discs were determined by measurements of advancing contact angle on the surface of polymers and their blends using the sessile drop method. The surface energy was determined by the OWRK method. Additionally, the mass swelling factor and hydration percentage of examined polymers and their blends in simulated biological fluids were evaluated. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of oxidation agent on wood biomass in ethylene vinyl acetate conductive polymer: tensile properties, tensile fracture surface and electrical properties

NASA Astrophysics Data System (ADS)

Hanif, M. P. M.; Supri, A. G.; Rozyanty, A. R.; Tan, S. J.

2017-10-01

The wood fiber (WF) type of Pulverised Wood Filler obtained by combustion process at temperature under 700 °C for 3 hours was characterized and coated with ferric chloride (FeCl3) by ethanol solution. Both carbonized wood fiber (CWF) and carbonized wood fiber-ferric chloride (CWF-FeCl3) were used as filler in ethylene vinyl acetate (EVA) conductive polymer. The filler was coated with FeCl3 to enhance the properties of the CWF to achieve progressive mechanical and electrical properties. The CWF and CWF-FeCl3 loading were varied from 2.5 to 10.0 wt%. EVA/CWF and EVA/CWF-FeCl3 conductive polymer were processed by using Brabender Plasticoder at 160 °C with 50 rpm rotor speed for 10 min. The mechanical properties were investigated by tensile testing and the tensile fractured surface of conductive polymers was analyzed by scanning electron microscopy (SEM) analysis. Then, the electrical conductivity of conductive polymer was determined by four-point probe I-V measurement system. The EVA/CWF-FeCl3 conductive polymer showed greater electrical conductivity and tensile strength but lower elongation at break than EVA/CWF conductive polymer. SEM morphology displayed rougher surface between CWF-FeCl3 and EVA phases compared to EVA/CWF conductive polymer.

Lattice-patterned LC-polymer composites containing various nanoparticles as additives

PubMed Central

2012-01-01

In this study, we show the effect of various nanoparticle additives on phase separation behavior of a lattice-patterned liquid crystal [LC]-polymer composite system and on interfacial properties between the LC and polymer. Lattice-patterned LC-polymer composites were fabricated by exposing to UV light a mixture of a prepolymer, an LC, and SiO2 nanoparticles positioned under a patterned photomask. This resulted in the formation of an LC and prepolymer region through phase separation. We found that the incorporation of SiO2 nanoparticles significantly affected the electro-optical properties of the lattice-patterned LC-polymer composites. This effect is a fundamental characteristic of flexible displays. The electro-optical properties depend on the size and surface functional groups of the SiO2 nanoparticles. Compared with untreated pristine SiO2 nanoparticles, which adversely affect the performance of LC molecules surrounded by polymer walls, SiO2 nanoparticles with surface functional groups were found to improve the electro-optical properties of the lattice-patterned LC-polymer composites by increasing the quantity of SiO2 nanoparticles. The surface functional groups of the SiO2 nanoparticles were closely related to the distribution of SiO2 nanoparticles in the LC-polymer composites, and they influenced the electro-optical properties of the LC molecules. It is clear from our work that the introduction of nanoparticles into a lattice-patterned LC-polymer composite provides a method for controlling and improving the composite's electro-optical properties. This technique can be used to produce flexible substrates for various flexible electronic devices. PMID:22222011

Investigating the properties and interaction mechanism of nano-silica in polyvinyl alcohol/polyacrylamide blends at an atomic level.

PubMed

Wei, Qinghua; Wang, Yanen; Wang, Shuzhi; Zhang, Yingfeng; Chen, Xiongbiao

2017-11-01

The nano-silica can be incorporated into polymers for improved mechanical properties. Notably, the interaction between nano-silica and polymer is of a microscopic phenomenon and thus, hard to observe and study by using experimental methods. Based on molecular dynamics, this paper presents a study on the properties and the interaction mechanism of nano-silica in the polyvinyl alcohol (PVA)/polyacrylamide (PAM) blends at an atomic level. Specifically, six blends of PVA/PAM with varying concentrations of nano-silica (0-13wt%) and two interfacial interaction models of polymers on the silica surface were designed and analyzed at an atomic level in terms of concentration profile, mechanical properties, fractional free volume (FFV), dynamic properties of polymers and X-ray diffraction patterns. The concentration profile results and micromorphologies of equilibrium models suggest PAM molecular chains are easier to be adsorbed on the silica surface than PVA molecular chains in blends. The incorporation of nano-silica into the PVA/PAM blends can increase the blend mechanical properties, densities, and semicrystalline character. Meanwhile, the FFV and the mobility of polymer chain decrease with the silica concentration, which agrees with the results of mechanical properties, densities, and semicrystalline character. Our results also illustrate that an analysis of binding energies and pair correlation functions (PCF) allows for the discovery of the interaction mechanism of nano-silica in PVA/PAM blends; and that hydrogen bond interactions between polar functional groups of polymer molecular chains and the hydroxyl groups of the silica surface are involved in adsorption of the polymers on the silica surface, thus affecting the interaction mechanism of nano-silica in PVA/PAM blend systems. Copyright © 2017 Elsevier Ltd. All rights reserved.

Multiple Ion Implantation Effects on Wear and Wet Ability of Polyethylene Based Polymers

NASA Astrophysics Data System (ADS)

Torrisi, L.; Visco, A. M.; Campo, N.

2004-10-01

Polyethylene based polymers were ion implanted with multiple irradiations of different ions (N+, Ar+ and Kr+) at energies between 30 keV and 300 keV and doses ranging between 1013 and 1016 ions/cm2. The ion implantation dehydrogenises the polyethylene inducing cross-link effects in the residual polymer carbons. At high doses the irradiated surface show properties similar to graphite surfaces. The depth of the modified layers depends on the ion range in polyethylene at the incident ion energy. The chemical modification depends on the implanted doses and on the specie of the incident ions. A "pin-on-disc" machine was employed to measure the polymer wear against AISI-316 L stainless steel. A "contact-angle-test" machine was employed to measure the wet ability of the polymer surface for 1 μl pure water drop. Measurements demonstrate that the multiple ion implantation treatments decrease the surface wear and the surface wetting and produce a more resistant polymer surface. The properties of the treated surfaces improves the polymer functionality for many bio-medical applications, such as those relative to the polyethylene friction discs employed in knee and hip prosthesis joints. The possibility to use multiply ion implantations of polymers with traditional ion implanters and with laser ion sources producing plasmas is investigated.

Effects of polymer surface energy on morphology and properties of silver nanowire fabricated via nanoimprint and E-beam evaporation

NASA Astrophysics Data System (ADS)

Zhao, Zhi-Jun; Hwang, Soon Hyoung; Jeon, Sohee; Jung, Joo-Yun; Lee, Jihye; Choi, Dae-Geun; Choi, Jun-Hyuk; Park, Sang-Hu; Jeong, Jun-Ho

2017-10-01

In this paper, we demonstrate that use of different nanoimprint resins as a polymer pattern has a significant effect on the morphology of silver (Ag) nanowires deposited via an E-beam evaporator. RM-311 and Ormo-stamp resins are chosen as a polymer pattern to form a line with dimensions of width (100 nm) × space (100 nm) × height (120 nm) by using nanoimprint lithography (NIL). Their contact angles are then measured to evaluate their surface energies. In order to compare the properties of the Ag nanowires deposited on the various polymer patterns with different surface energies, hydrophobic surface treatment of the polymer pattern surface is implemented using self-assembled monolayers. In addition, gold and aluminum nanowires are fabricated for comparison with the Ag nanowires, with the differences in the nanowire morphologies being determined by the different atomic properties. The monocrystalline and polycrystalline structures of the various Ag nanowire formations are observed using transmission electron microscopy. In addition, the melting temperatures and optical properties of four kinds of Ag nanowire morphologies deposited on various polymer patterns are evaluated using a hot plate and an ultraviolet-visible (UV-vis) spectrometer, respectively. The results indicate that the morphology of the Ag nanowire determines the melting temperature and the transmission. We believe that these findings will greatly aid the development of NIL, along with physical evaporation and chemical deposition techniques, and will be widely employed in optics, biology, and surface wettability applications.

Progress in Preparation of Monodisperse Polymer Microspheres

NASA Astrophysics Data System (ADS)

Zhang, Hongyan

2017-12-01

The monodisperse crosslinked polymer microspheres have attracted much attention because of their superior thermal and solvent resistance, mechanical strength, surface activity and adsorption properties. They are of wide prospects for using in many fields such as biomedicine, electronic science, information technology, analytical chemistry, standard measurement and environment protection etc. Functional polymer microspheres prepared by different methods have the outstanding surface property, quantum size effect and good potential future in applications with its designable structure, controlled size and large ratio of surface to volume. Scholars of all over the world have focused on this hot topic. The preparation method and research progress in functional polymer microspheres are addressed in the paper.

Structures and Properties of Polymers Important to Their Wear Behavior

NASA Technical Reports Server (NTRS)

Tanaka, K.

1984-01-01

The wear and transfer of various semicrystalline polymers sliding against smooth steel or glass surfaces were examined. The effects of structures, and properties of polymers on their wear behavior are discussed. It is found that the high wear characteristics of PTFE is due to the easy destruction of the banded structure of PTFE. The size of spherulites and the molecular profile are closely related to the magnitude of wear rates of typical semicrystalline polymers. The effects of these factors on the wear rate on the basis of the destruction or melting of spherulites at the frictional surface are discussed. Although the fatigue theory of wear indicates that some mechanical properties are important to wear behavior, it is shown that the theory does not always explain the experimental result obtained on a smooth surface.

Modification of surface characteristic and tribo-electric properties of polymers by DBD plasma in atmospheric air

NASA Astrophysics Data System (ADS)

Bekkara, Mohammed Fethi; Dascalescu, Lucien; Benmimoun, Youcef; Zeghloul, Thami; Tilmatine, Amar; Zouzou, Noureddine

2018-01-01

The aim of this paper is to quantify the effects of dielectric barrier discharge (DBD) exposure on the physico-chemical and tribo-electric properties of polymers. The study was conducted in atmospheric air on polypropylene, polyethylene and polyvinyl-chloride. These three types of polymers are widely used in industry. The polymers were characterized by means of an optical profilometer, a fourier-transform infrared (FTIR) spectrometer and an electric charge measurement system. The latter is composed of a Faraday pail connected to an electrometer. The profilometer analyses showed that the DBD plasma treatment has increased the surface roughness of the three polymers. FTIR revealed that oxygen atoms and polar groups were grafted on their surfaces, thereby conferring them a hydrophilic character. The short (2 sec) DBD plasma treatment has considerably improved the electrostatic charge acquired by the polymers during electrostatic tribo-charging, while longer exposures conferred the polymer anti-static properties and decreased its tribo-charging capability. The correlation between the results of the physico-chemical analyses and the tribo-electric behavior has been discussed.

Electrowetting of Weak Polyelectrolyte-Coated Surfaces.

PubMed

Sénéchal, Vincent; Saadaoui, Hassan; Rodriguez-Hernandez, Juan; Drummond, Carlos

2017-05-23

Polymer coatings are commonly used to modify interfacial properties like wettability, lubrication, or biocompatibility. These properties are determined by the conformation of polymer molecules at the interface. Polyelectrolytes are convenient elementary bricks to build smart materials, given that polyion chain conformation is very sensitive to different environmental variables. Here we discuss the effect of an applied electric field on the properties of surfaces coated with poly(acrylic acid) brushes. By combining atomic force microscopy, quartz crystal microbalance, and contact angle experiments, we show that it is possible to precisely tune polyion chain conformation, surface adhesion, and surface wettability using very low applied voltages if the polymer grafting density and environmental conditions (pH and ionic strength) are properly formulated. Our results indicate that the effective ionization degree of the grafted weak polyacid can be finely controlled with the externally applied field, with important consequences for the macroscopic surface properties.

Ultrasonic-assisted synthesis of polyvinyl alcohol/phytic acid polymer film and its thermal stability, mechanical properties and surface resistivity.

PubMed

Li, Jihui; Li, Yongshen; Song, Yunna; Niu, Shuai; Li, Ning

2017-11-01

In this paper, polyvinyl alcohol/phytic acid polymer (PVA/PA polymer) was synthesized through esterification reaction of PVA and PA in the case of acidity and ultrasound irradiation and characterized, and PVA/PA polymer film was prepared by PVA/PA polymer and characterized, and the influence of dosage of PA on the thermal stability, mechanical properties and surface resistivity of PVA/PA polymer film were researched, and the influence of sonication time on the mechanical properties of PVA/PA polymer film was investigated. Based on those, it was concluded that the hydroxyl group on the chain of PVA and the phosphonic group on PA were connected together in the form of phosphonate bond, and the hydroxyl group on the chain of PVA were connected together in the form of ether bond after the intermolecular dehydration; in the meantime, it was also confirmed that PVA/PA polymer film prepared from 1.20mL of PA not only had the high thermal stability and favorable ductility but also the low surface resistivity in comparison with PVA/PA polymer film with 0.00mL of PA, and the ductility of PVA/PA polymer film was very sensitive to the sonication time. Copyright © 2017. Published by Elsevier B.V.

Active screen cage pulsed dc discharge for implanting copper in polytetrafluoroethylene (PTFE)

NASA Astrophysics Data System (ADS)

Zaka-ul-Islam, Mujahid; Naeem, Muhammad; Shafiq, Muhammad; Sitara; Jabbar Al-Rajab, Abdul; Zakaullah, Muhammad

2017-07-01

Polymers such as polytetrafluoroethylene (PTFE) are widely used in artificial organs where long-term anti-bacterial properties are required to avoid bacterial proliferation. Copper or silver ion implantation on the polymer surface is known as a viable method to generate long-term anti-bacterial properties. Here, we have tested pulsed DC plasma with copper cathodic cage for the PTFE surface treatment. The surface analysis of the treated specimens suggests that the surface, structural properties, crystallinity and chemical structure of the PTFE have been changed, after the plasma treatment. The copper release tests show that copper ions are released from the polymer at a slow rate and quantity of the released copper increases with the plasma treatment time.

Amphiphilic polymer based on fluoroalkyl and PEG side chains for fouling release coating

NASA Astrophysics Data System (ADS)

Cong, W. W.; Wang, K.; Yu, X. Y.; Zhang, H. Q.; Lv, Z.; Gui, T. J.

2017-12-01

Under static conditions, fouling release coating could not express good release property to marine organisms. Amphiphilic polymer with mixture of fluorinated monomer and short side group of polyethylene glycol (PEG) was synthesized. And also we studied the ability of amphiphilic polymer to influence the surface properties and how it controlled the adhesion of marine organisms to coated surfaces. By incorporating fluorinated monomer and PEG side chain into the polymer, the effect of incorporating both polar and non-polar groups on fouling-release coating could be studied. The dry surface was characterized by three-dimensional digital microscopy and scanning electron microscopy (SEM), and the morphology of the amphiphilic fouling release coating showed just like flaky petal. The amphiphilic polymer in fouling release coating tended to reconstruct in water, and the ability was examined by static contact angle, which was smaller than the PDMS (polydimethylsiloxane) fouling release coating. Also surface energy was calculated by three solvents, and surface energy of amphiphilic fouling release coating was higher than that of the PDMS fouling release coating. To understand more about its fouling release property, seawater exposure method was adopted in gulf of Qingdao port. Fewer diatoms Navicula were found in biofilm after using amphiphilic fouling release coating. In general, coating containing both PEG and fluorinated side chain possessed certain fouling release property.

Ferrocene Containing Copolymers with Improved Electrostatic Dissipation Properties for Advanced Applications

NASA Technical Reports Server (NTRS)

Smith, T. M.; Nelson, G. L.

2005-01-01

Electrostatic dissipative polymers are used for a variety of functions. Typical methods utilized to transform electrically insulating polymers into either charge dissipative or conductive materials involve incorporating a conductive filler, conductive polymer, oxidizing the surface using plasma, or incorporating surfactants that act as surface wetting agents. Another approach is to synthesize a block copolymer that is expected to result in better electrical properties with minimal impacts to physical, fire, and thermal properties. One such block that can be added into the main chain of polymers is a diol terminated ferrocene oligomer, which is expected to impart electrostatic dissipative properties into the host polymer while concurrently improving the overall fire properties. Previous work with polyurethanes incorporating a ferrocene oligomer into the main chain resulted in much improved fire retardancy. In dealing with electrostatic dissipative materials the important questions are: how easily does the material charge and how quickly can the charge move to ground. One normally describes the materials conductivity, but conductivity only measures the fastest path for an electron not the slowest path. The slowest path is the one of interest, since it is left on the surface and thus can cause discharges. In order to assess ease of charging and decay times corona charge dissipation measurements can accurately assess these properties by introducing a charge on the surface of the material then measuring the surface voltage and the amount of charge deposited. The charge decay curve then will give an indication of a materials electrostatic dissipation properties. Normally, triboelectric testing can be performed, but results vary. Corona charge dissipation results are more repeatable.

Harnessing of radio frequency discharge for production of biologically compatible coatings for ophthalmology

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

Abdullin, I.Sh.; Bragin, V.E.; Bykanov, A.N.

Gas discharge plasma modification of polymer materials and metals is one of the known physical approaches for improving of materials biocompatibility in ophthalmology and surgery. The surface treatment in RF discharges can be effectively realized in the discharge afterglow and in the discharge region itself too. This modification method is more convenient and produces more uniform surfaces in comparison with other discharge types. The carried out experiments and published up to now results show that interaction of UV radiation, fluxes of ions, electrons and metastable particles with material`s surface changes chemical composition and surface structure. The exerting of these agentsmore » on the sample surface produces the following effects. There are processes of physical and plasma-chemical surface etching producing effective surface cleaning of different types of contaminations. It may be surface contaminations by hydrocarbons because of preliminary surface contacts with biological or physical bodies. It may be surface contaminations caused by characteristic properties of chemical technology too. There is a surface layer with thickness from some angstroms up to few hundreds of angstroms. The chemical content and structure of this layer is distinguished from the bulk polymer properties. The presence of such {open_quotes}technological{close_quotes} contaminations produces the layer of material substantially differing from the base polymer. The basic layer physical and chemical properties for example, gas permeation rate may substantially differ from the base polymer. Attempts to clean the surface from these contaminations by chemical methods (solutions) have not been successful and produced contaminations of more deep polymer layers. So the plasma cleaning is the most profitable method of polymer treatment for removing the surface contaminations. The improving of wettability occurs during this stage of treatment.« less

Polyethylene oxide hydration in grafted layers

NASA Astrophysics Data System (ADS)

Dormidontova, Elena; Wang, Zilu

Hydration of water soluble polymers is one of the key-factors defining their conformation and properties, similar to biopolymers. Polyethylene oxide (PEO) is one of the most important biomedical-applications polymers and is known for its reverse temperature solubility due to hydrogen bonding with water. As in many practical applications PEO chains are grafted to surfaces, e.g. of nanoparticles or planar surfaces, it is important to understand PEO hydration in such grafted layers. Using atomistic molecular dynamic simulations we investigate the details of molecular conformation and hydration of PEO end-grafted to gold surfaces. We analyze polymer and water density distribution as a function of distance from the surface for different grafting densities. Based on a detailed analysis of hydrogen bonding between polymer and water in grafted PEO layers, we will discuss the extent of PEO hydration and its implication for polymer conformation, mobility and layer properties. This research is supported by NSF (DMR-1410928).

Polymerization Behavior and Polymer Properties of Eosin-Mediated Surface Modification Reactions.

PubMed

Avens, Heather J; Randle, Thomas James; Bowman, Christopher N

2008-10-17

Surface modification by surface-mediated polymerization necessitates control of the grafted polymer film thicknesses to achieve the desired property changes. Here, a microarray format is used to assess a range of reaction conditions and formulations rapidly in regards to the film thicknesses achieved and the polymerization behavior. Monomer formulations initiated by eosin conjugates with varying concentrations of poly(ethylene glycol) diacrylate (PEGDA), N-methyldiethanolamine (MDEA), and 1-vinyl-2-pyrrolidone (VP) were evaluated. Acrylamide with MDEA or ascorbic acid as a coinitiator was also investigated. The best formulation was found to be 40 wt% acrylamide with MDEA which yielded four to eight fold thicker films (maximum polymer thickness increased from 180 nm to 1420 nm) and generated visible films from 5-fold lower eosin surface densities (2.8 vs. 14 eosins/µm(2)) compared to a corresponding PEGDA formulation. Using a microarray format to assess multiple initiator surface densities enabled facile identification of a monomer formulation that yields the desired polymer properties and polymerization behavior across the requisite range of initiator surface densities.

Polymerization Behavior and Polymer Properties of Eosin-Mediated Surface Modification Reactions

PubMed Central

Avens, Heather J.; Randle, Thomas James; Bowman, Christopher N.

2008-01-01

Surface modification by surface-mediated polymerization necessitates control of the grafted polymer film thicknesses to achieve the desired property changes. Here, a microarray format is used to assess a range of reaction conditions and formulations rapidly in regards to the film thicknesses achieved and the polymerization behavior. Monomer formulations initiated by eosin conjugates with varying concentrations of poly(ethylene glycol) diacrylate (PEGDA), N-methyldiethanolamine (MDEA), and 1-vinyl-2-pyrrolidone (VP) were evaluated. Acrylamide with MDEA or ascorbic acid as a coinitiator was also investigated. The best formulation was found to be 40 wt% acrylamide with MDEA which yielded four to eight fold thicker films (maximum polymer thickness increased from 180 nm to 1420 nm) and generated visible films from 5-fold lower eosin surface densities (2.8 vs. 14 eosins/µm2) compared to a corresponding PEGDA formulation. Using a microarray format to assess multiple initiator surface densities enabled facile identification of a monomer formulation that yields the desired polymer properties and polymerization behavior across the requisite range of initiator surface densities. PMID:19838291

Novel adhesive properties of poly(ethylene-oxide) adsorbed nanolayers

NASA Astrophysics Data System (ADS)

Zeng, Wenduo

Solid-polymer interfaces play crucial roles in the multidisciplinary field of nanotechnology and are the confluence of physics, chemistry, biology, and engineering. There is now growing evidence that polymer chains irreversibly adsorb even onto weakly attractive solid surfaces, forming a nanometer-thick adsorbed polymer layer ("adsorbed polymer nanolayers"). It has also been reported that the adsorbed layers greatly impact on local structures and properties of supported polymer thin films. In this thesis, I aim to clarify adhesive and tribological properties of adsorbed poly(ethylene-oxide) (PEO) nanolayers onto silicon (Si) substrates, which remain unsolved so far. The adsorbed nanolayers were prepared by the established protocol: one has to equilibrate the melt or dense solution against a solid surface; the unadsorbed chains can be then removed by a good solvent, while the adsorbed chains are assumed to maintain the same conformation due to the irreversible freezing through many physical solid-segment contacts. I firstly characterized the formation process and the surface/film structures of the adsorbed nanolayers by using X-ray reflectivity, grazing incidence X-ray diffraction, and atomic force microscopy. Secondly, to compare the surface energy of the adsorbed layers with the bulk, static contact angle measurements with two liquids (water and glycerol) were carried out using a optical contact angle meter equipped with a video camera. Thirdly, I designed and constructed a custom-built adhesion-testing device to quantify the adhesive property. The experimental results provide new insight into the microscopic structure - macroscopic property relationship at the solid-polymer interface.

Understanding the surface properties and rheology of a silica suspension mediated by a comb-type poly(acrylic acid)/poly(ethylene oxide) (PAA/PEO) copolymer: effect of salinity.

PubMed

Yang, Dingzheng; Yan, Bin; Xiang, Li; Xu, Haolan; Wang, Xiaogang; Zeng, Hongbo

2018-06-13

Understanding the surface properties and rheology of colloidal suspensions in the presence of polymer additives with high salinity are of great importance in formulating construction materials and optimizing process conditions in the mining and petroleum industry. In this work, the surface properties and rheology of a model spherical silica aqueous suspension mediated by a comb-type poly(acrylic acid)/poly(ethylene oxide) (PAA/PEO) copolymer at various salt concentrations have been investigated. Adsorption measurements using a Quartz Crystal Microbalance with Dissipation monitoring (QCM-D) align well with zeta potential tests and show that polymer adsorption on silica surfaces is enhanced at high salinity (i.e., 3 M NaCl) than at low salinity (i.e., 1 mM NaCl) due to the suppression of the electrical double layer. Surface Forces Apparatus (SFA) measurements reveal that for interactions between two mica surfaces (the basal plane of which has a similar structure as silica) at a high polymer concentration (e.g., 2 wt%), steric repulsion dominates in 1 mM NaCl while bridging attraction is observed in 3 M NaCl. Surface force measurements agree with rheological results on silica suspensions with 0.5 to 2 wt% of PAA/PEO addition, which shows a significant decrease in yield stress in 1 mM NaCl due to steric repulsion but an insignificant variation in yield stress in 3 M NaCl due to attractive bridging interactions. This work provides useful information regarding the surface properties and rheological properties of comb-type polymer-mediated silica suspensions under different salinity conditions, with implications on designing and processing complex colloidal suspensions with polymer additives for various applications.

Do Membranes Dream of Electric Tubes? Advanced Membranes Using Carbon Nanotube - Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

de Lannoy, Charles-Francois Pedro Claude Karolek Ghislain

Membrane technologies represent an energy efficient, effective solution for treating municipal and commercial waters/wastewaters. Membranes are predominantly polymer-based and despite steady advances in polymeric materials, they continue to suffer from operational problems including biofouling and breakages. This work addresses these two disparate problems by developing novel CNT-polymer nanocomposite materials that contain variously functionalized carbon nanotubes (fCNTs) in low quantities (<0.5wt%). Several strategies have been employed to achieve highly functional CNT-polymer nanocomposite membranes including blend mixing, ionic charge association, and covalent cross-linking with monomer and oligomer constituents. These CNT-polymer nanocomposite membranes were compared to traditional polymer membranes across various properties including increased Young's Modulus, changes in surface hydrophilicity, fine control over molecular weight cut-off and flux, and surface electrical conductivity. Membranes with high surface electrical conductivity were further tested for their anti-biofouling properties. Finally, CNT stability and polymer compatibility were evaluated throughout membrane manufacture, use, and cleaning. The incorporation of CNTs mixed in bulk phase and linked through ionic associations in polymer matrices showed significant (50%) increases in Young's modulus for certain CNT functionalizations and derivatization percent. Membranes formed with high surface electrical conductivity demonstrated almost complete resistance to biofouling (> 95%) in long-term bacterially challenged experiments. CNTs and polymer mixtures that lacked covalent or ionic bonds were susceptible to significant (up to 10%) loss of CNTs during membrane non-solvent gelation and aggressive chemical cleaning treatment. Functionalized carbon nanotubes endow polymer membranes with their unique strength and electrically conductive properties. These added properties were demonstrated to greatly improve membrane operational efficiency and membrane longevity. CNT-polymer nanocomposite membranes offer low-energy, high-efficiency, and long-lifetime alternatives to traditional polymer membranes. With further advances in polymeric nanomaterials, membrane technology has the potential for wide applicability across many fields outside of water filtration and desalination.

Influence of the Surfactant Structure on Photoluminescent π-Conjugated Polymer Nanoparticles: Interfacial Properties and Protein Binding.

PubMed

Urbano, Laura; Clifton, Luke; Ku, Hoi Ki; Kendall-Troughton, Hannah; Vandera, Kalliopi-Kelli A; Matarese, Bruno F E; Abelha, Thais; Li, Peixun; Desai, Tejal; Dreiss, Cécile A; Barker, Robert D; Green, Mark A; Dailey, Lea Ann; Harvey, Richard D

2018-05-17

π-Conjugated polymer nanoparticles (CPNs) are under investigation as photoluminescent agents for diagnostics and bioimaging. To determine whether the choice of surfactant can improve CPN properties and prevent protein adsorption, five nonionic polyethylene glycol alkyl ether surfactants were used to produce CPNs from three representative π-conjugated polymers. The surfactant structure did not influence size or yield, which was dependent on the nature of the conjugated polymer. Hydrophobic interaction chromatography, contact angle, quartz crystal microbalance, and neutron reflectivity studies were used to assess the affinity of the surfactant to the conjugated polymer surface and indicated that all surfactants were displaced by the addition of a model serum protein. In summary, CPN preparation methods which rely on surface coating of a conjugated polymer core with amphiphilic surfactants may produce systems with good yields and colloidal stability in vitro, but may be susceptible to significant surface alterations in physiological fluids.

Chemical anchoring of organic conducting polymers to semiconducting surfaces

DOEpatents

Frank, A.J.; Honda, K.

1984-01-01

According to the present invention, an improved method of coating electrodes with conductive polymer films and/or preselected catalysts is provided. The charge conductive polymer is covalently or coordinatively attached to the electrode surface to strengthen the adhesion characteristics of the polymer to the electrode surface or to improve charge conductive properties between the conductive polymer and the electrode surface. Covalent or coordinative attachment is achieved by a number of alternative methods including covalently or coordinatively attaching the desired monomer to the electrode by means of a suitable coupling reagent and, thereafter, electrochemically polymerizing the monomer in situ.

Chemical anchoring of organic conducting polymers to semiconducting surfaces

DOEpatents

Frank, Arthur J.; Honda, Kenji

1984-01-01

According to the present invention, an improved method of coating electrodes with conductive polymer films and/or preselected catalysts is provided. The charge-conductive polymer is covalently or coordinatively attached to the electrode surface to strengthen the adhesion characteristics of the polymer to the electrode surface or to improve charge-conductive properties between the conductive polymer and the electrode surface. Covalent or coordinative attachment is achieved by a number of alternative methods including covalently or coordinatively attaching the desired monomer to the electrode by means of a suitable coupling reagent and, thereafter, electrochemically polymerizing the monomer in situ.

Preparation and antifouling properties of 2-(meth-acryloyloxy)ethyl cholinephosphate based polymers modified surface with different molecular architectures by ATRP.

PubMed

Jiang, Yuchen; Su, Yuling; Zhao, Lili; Meng, Fancui; Wang, Quanxin; Ding, Chunmei; Luo, Jianbin; Li, Jianshu

2017-08-01

Choline phosphate (CP) containing polymers modified surfaces have been shown good resist to the adhesion of proteins while prompt the attaching of mammalian cells due to the dipole pairing between the CP groups of the polymer and the phosphorylcholine (PC) groups on the cell membrane. However, the antifouling activities of CP modified surface against microbes have not been investigated at present. In addition, CP containing polymers modified surface with different molecular architectures has not been prepared and studied. To this end, glass slides surface modified with two different 2-(meth-acryloyloxy)ethyl cholinephosphate (MCP) containing polymer (PMCP) structures, i.e. brush-like (Glass-PMCP) and bottle brush-like (Glass-PHEMA-g-PMCP) architectures, were prepared in this work by surface-initiated atom transfer radical polymerization (SI-ATRP). The surface physichemical and antifouling properties of the prepared surfaces were characterized and studied. The Glass-PMCP shows improved antifouling properties against proteins and bacteria as compared to pristine glass slides (Glass-OH) and glass slides grafted with poly(2-hydroxyethyl methacrylate) (Glass-PHEMA). Notably, a synergetic fouling resistant properties of PHEMA and PMCP is presented for Glass-PHEMA-g-PMCP, which shows superior antifouling activities over Glass-PHEMA and Glass-PMCP. Furthermore, glass slides containing PMCP, i.e. Glass-PMCP and Glas-PHEMA-g-PMCP, decrease platelet adhesion and prevent their activation significantly. Therefore, the combination of antifouling PHEMA and PMCP into one system holds potential for prevention of bacterial fouling and biomaterial-centered infections. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of polymer graft properties on protein adsorption and transport in ion exchange chromatography: a multiscale modeling study.

PubMed

Basconi, Joseph E; Carta, Giorgio; Shirts, Michael R

2015-04-14

Multiscale simulation is used to study the adsorption of lysozyme onto ion exchangers obtained by grafting charged polymers into a porous matrix, in systems with various polymer properties and strengths of electrostatic interaction. Molecular dynamics simulations show that protein partitioning into the polymer-filled pore space increases with the overall charge content of the polymers, while the diffusivity in the pore space decreases. However, the combination of greatly increased partitioning and modestly decreased diffusion results in macroscopic transport rates that increase as a function of charge content, as the large concentration driving force due to enhanced pore space partitioning outweighs the reduction in the pore space diffusivity. Matrices having greater charge associated with the grafted polymers also exhibit more diffuse intraparticle concentration profiles during transient adsorption. In systems with a high charge content per polymer and a low protein loading, the polymers preferentially partition toward the surface due to favorable interactions with the surface-bound protein. These results demonstrate the potential of multiscale modeling to illuminate qualitative trends between molecular properties and the adsorption equilibria and kinetic properties observable on macroscopic scales.

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

Reversible switching of wetting properties and erasable patterning of polymer surfaces using plasma oxidation and thermal treatment

NASA Astrophysics Data System (ADS)

Rashid, Zeeshan; Atay, Ipek; Soydan, Seren; Yagci, M. Baris; Jonáš, Alexandr; Yilgor, Emel; Kiraz, Alper; Yilgor, Iskender

2018-05-01

Polymer surfaces reversibly switchable from superhydrophobic to superhydrophilic by exposure to oxygen plasma and subsequent thermal treatment are demonstrated. Two inherently different polymers, hydrophobic segmented polydimethylsiloxane-urea copolymer (TPSC) and hydrophilic poly(methyl methacrylate) (PMMA) are modified with fumed silica nanoparticles to prepare superhydrophobic surfaces with roughness on nanometer to micrometer scale. Smooth TPSC and PMMA surfaces are also used as control samples. Regardless of their chemical structure and surface topography, all surfaces display completely reversible wetting behavior changing from hydrophobic to hydrophilic and back for many cycles upon plasma oxidation followed by thermal annealing. Influence of plasma power, plasma exposure time, annealing temperature and annealing time on the wetting behavior of polymeric surfaces are investigated. Surface compositions, textures and topographies are characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and white light interferometry (WLI), before and after oxidation and thermal annealing. Wetting properties of the surfaces are determined by measuring their static, advancing and receding water contact angle. We conclude that the chemical structure and surface topography of the polymers play a relatively minor role in reversible wetting behavior, where the essential factors are surface oxidation and migration of polymer molecules to the surface upon thermal annealing. Reconfigurable water channels on polymer surfaces are produced by plasma treatment using a mask and thermal annealing cycles. Such patterned reconfigurable hydrophilic regions can find use in surface microfluidics and optofluidics applications.

Electrokinetic properties of polymer colloids

NASA Technical Reports Server (NTRS)

Micale, F. J.; Fuenmayor, D. Y.

1986-01-01

The surface of polymer colloids, especially polystyrene latexes, were modified for the purpose of controlling the electrokinetic properties of the resulting colloids. Achievement required a knowledge of electrical double layer charging mechanism, as a function of the electrolyte conditions, at the polymer/water interface. The experimental approach is to control the recipe formulation in the emulsion polymerization process so as to systematically vary the strong acid group concentration on the surface of the polymer particles. The electrophoretic mobility of these model particles will then be measured as a function of surface group concentration and as a function of electrolyte concentration and type. An effort was also made to evaluate the electrophoretic mobility of polystyrene latexes made in space and to compare the results with latexes made on the ground.

Atomic Origins of the Self-Healing Function in Cement–Polymer Composites

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

Nguyen, Manh-Thuong; Wang, Zheming; Rod, Kenton A.

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized towards defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement/polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties ofmore » these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG spectroscopy.« less

Atomic Origins of the Self-Healing Function in Cement-Polymer Composites.

PubMed

Nguyen, Manh-Thuong; Wang, Zheming; Rod, Kenton A; Childers, M Ian; Fernandez, Carlos; Koech, Phillip K; Bennett, Wendy D; Rousseau, Roger; Glezakou, Vassiliki-Alexandra

2018-01-24

Motivated by recent advances in self-healing cement and epoxy polymer composites, we present a combined ab initio molecular dynamics and sum frequency generation (SFG) vibrational spectroscopy study of a calcium-silicate-hydrate/polymer interface. On stable, low-defect surfaces, the polymer only weakly adheres through coordination and hydrogen bonding interactions and can be easily mobilized toward defected surfaces. Conversely, on fractured surfaces, the polymer strongly anchors through ionic Ca-O bonds resulting from the deprotonation of polymer hydroxyl groups. In addition, polymer S-S groups are turned away from the cement-polymer interface, allowing for the self-healing function within the polymer. The overall elasticity and healing properties of these composites stem from a flexible hydrogen bonding network that can readily adapt to surface morphology. The theoretical vibrational signals associated with the proposed cement-polymer interfacial chemistry were confirmed experimentally by SFG vibrational spectroscopy.

Cyclic Polymers: From Scientific Curiosity to Advanced Materials for Gene Delivery and Surface Modification.

PubMed

Verbraeken, Bart; Hoogenboom, Richard

2017-06-12

Cyclic versus linear: The superiority of cyclic polymers over their linear counterparts is highlighted. Cyclic poly(2-oxazoline)s have been shown to provide excellent shielding properties when grafted to TiO 2 surfaces and Fe 3 O 4 nanoparticles owing to their ultrahigh grafting densities leading to low friction surfaces, superior antifouling properties, and extreme nanoparticle stabilization. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Efficient synthetic access to thermo-responsive core/shell nanoparticles

NASA Astrophysics Data System (ADS)

Dine, Enaam Jamal Al; Ferjaoui, Zied; Roques-Carmes, Thibault; Schjen, Aleksandra; Meftah, Abdelaziz; Hamieh, Tayssir; Toufaily, Joumana; Schneider, Raphaël; Gaffet, Eric; Alem, Halima

2017-03-01

Core/shell nanostructures based on silica, fluorescent ZnO quantum dots (QDs) and superparamagnetic Fe3O4 nanoparticles (NPs) were prepared and fully characterized by the combination of different techniques and the physical properties of the nanostructures were studied. We demonstrate the efficiency of the atom transfer radical polymerization with activators regenerated by electron transfer process to graft (co-)polymers of different structures and polarity at the surface of metal oxide NPs. The influence of the polymer chain configuration on the optical properties of the ZnO/polymer core/shell QDs was enlightened. Concerning the magnetic properties of the Fe3O4/polymer nanostructures, only the amount of the grafted polymer plays a role on the saturation magnetization of the NPs and no influence of the aggregation was evidenced. The simple and fast process described in this work is efficient for the grafting of copolymers from surfaces and the derived NPs display the combination of the physical properties of the core and the macromolecular behavior of the shell.

Efficient synthetic access to thermo-responsive core/shell nanoparticles.

PubMed

Dine, Enaam Jamal Al; Ferjaoui, Zied; Roques-Carmes, Thibault; Schjen, Aleksandra; Meftah, Abdelaziz; Hamieh, Tayssir; Toufaily, Joumana; Schneider, Raphaël; Gaffet, Eric; Alem, Halima

2017-03-24

Core/shell nanostructures based on silica, fluorescent ZnO quantum dots (QDs) and superparamagnetic Fe 3 O 4 nanoparticles (NPs) were prepared and fully characterized by the combination of different techniques and the physical properties of the nanostructures were studied. We demonstrate the efficiency of the atom transfer radical polymerization with activators regenerated by electron transfer process to graft (co-)polymers of different structures and polarity at the surface of metal oxide NPs. The influence of the polymer chain configuration on the optical properties of the ZnO/polymer core/shell QDs was enlightened. Concerning the magnetic properties of the Fe 3 O 4 /polymer nanostructures, only the amount of the grafted polymer plays a role on the saturation magnetization of the NPs and no influence of the aggregation was evidenced. The simple and fast process described in this work is efficient for the grafting of copolymers from surfaces and the derived NPs display the combination of the physical properties of the core and the macromolecular behavior of the shell.

Effect of polymer properties and adherend surfaces on adhesion. [titanium, aluminum

NASA Technical Reports Server (NTRS)

Dwight, D. W.; Counts, M. E.; Wightman, J. P.

1975-01-01

The surface properties associated with good adhesive joints were evaluated in terms of application of adhesive bonding in aerospace technology. The physical and chemical nature was determined of Ti and Al adherend surfaces after various surface treatments, and the effects on fracture surfaces of high temperature aging, and variations in amide, anhydride, and solvent during polymer synthesis. The effects were characterized of (1) high temperature during shear strength testing, (2) fiber-reinforced composites as adherends, (3) acid/base nature of adherends, (4) aluminum powder adhesive filler, and (5) bonding pressure.

Current Progress of Nanomaterials in Molecularly Imprinted Electrochemical Sensing.

PubMed

Zhong, Chunju; Yang, Bin; Jiang, Xinxin; Li, Jianping

2018-01-02

Nanomaterials have received much attention during the past decade because of their excellent optical, electronic, and catalytic properties. Nanomaterials possess high chemical reactivity, also high surface energy. Thus, provide a stable immobilization platform for biomolecules, while preserving their reactivity. Due to the conductive and catalytic properties, nanomaterials can also enhance the sensitivity of molecularly imprinted electrochemical sensors by amplifying the electrode surface, increasing the electron transfer, and catalyzing the electrochemical reactions. Molecularly imprinted polymers that contain specific molecular recognition sites can be designed for a particular target analyte. Incorporating nanomaterials into molecularly imprinted polymers is important because nanomaterials can improve the response signal, increase the sensitivity, and decrease the detection limit of the sensors. This study describes the classification of nanomaterials in molecularly imprinted polymers, their analytical properties, and their applications in the electrochemical sensors. The progress of the research on nanomaterials in molecularly imprinted polymers and the application of nanomaterials in molecularly imprinted polymers is also reviewed.

Smart Polymers with Special Wettability.

PubMed

Chang, Baisong; Zhang, Bei; Sun, Taolei

2017-01-01

Surface wettability plays a key role in addressing issues ranging from basic life activities to our daily life, and thus being able to control it is an attractive goal. Learning from nature, both of its structure and function, brings us much inspiration in designing smart polymers to tackle this major challenge. Life functions particularly depend on biomolecular recognition-induced interfacial properties from the aqueous phase onto either "soft" cell and tissue or "hard" inorganic bone and tooth surfaces. The driving force is noncovalent weak interactions rather than strong covalent combinations. An overview is provided of the weak interactions that perform vital actions in mediating biological processes, which serve as a basis for elaborating multi-component polymers with special wettabilities. The role of smart polymers from molecular recognitions to macroscopic properties are highlighted. The rationale is that highly selective weak interactions are capable of creating a dynamic synergetic communication in the building components of polymers. Biomolecules could selectively induce conformational transitions of polymer chains, and then drive a switching of physicochemical properties, e.g., roughness, stiffness and compositions, which are an integrated embodiment of macroscopic surface wettabilities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Use of Atmospheric-Pressure Plasma Jet for Polymer Surface Modification: An Overview

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

Kuettner, Lindsey A.

Atmospheric-pressure plasma jets (APPJs) are playing an increasingly important role in materials processing procedures. Plasma treatment is a useful tool to modify surface properties of materials, especially polymers. Plasma reacts with polymer surfaces in numerous ways thus the type of process gas and plasma conditions must be explored for chosen substrates and materials to maximize desired properties. This report discusses plasma treatments and looks further into atmospheric-pressure plasma jets and the effects of gases and plasma conditions. Following the short literature review, a general overview of the future work and research at Los Alamos National Laboratory (LANL) is discussed.

Remote Determination of Time-Dependent Stiffness of Surface-Degrading-Polymer Scaffolds Via Synchrotron-Based Imaging.

PubMed

Bawolin, N K; Chen, X B

2017-04-01

Surface-degrading polymers have been widely used to fabricate scaffolds with the mechanical properties appropriate for tissue regeneration/repair. During their surface degradation, the material properties of polymers remain approximately unchanged, but the scaffold geometry and thus mechanical properties vary with time. This paper presents a novel method to determine the time-dependent mechanical properties, particularly stiffness, of scaffolds from the geometric changes captured by synchrotron-based imaging, with the help of finite element analysis (FEA). Three-dimensional (3D) tissue scaffolds were fabricated from surface-degrading polymers, and during their degradation, the tissue scaffolds were imaged via the synchrotron-based imaging to characterize their changing geometry. On this basis, the stiffness behavior of scaffolds was estimated from the FEA, and the results obtained were compared to the direct measurements of scaffold stiffness from the load-displacement material testing. The comparison illustrates that the Young's moduli estimated from the FEA and characterized geometry are in agreement with the ones of direct measurements. The developed method of estimating the mechanical behavior was also demonstrated effective with a nondegrading scaffold that displays the nonlinear stress-strain behavior. The in vivo monitoring of Young's modulus by morphology characterization also suggests the feasibility of characterizing experimentally the difference between in vivo and in vitro surface degradation of tissue engineering constructs.

Surface energy characteristics of zeolite embedded PVDF nanofiber films with electrospinning process

NASA Astrophysics Data System (ADS)

Kang, Dong Hee; Kang, Hyun Wook

2016-11-01

Electrospinning is a nano-scale fiber production method with various polymer materials. This technique allows simple fiber diameters control by changing the physical conditions such as applied voltage and polymer solution viscosity during the fabrication process. The electrospun polymer fibers form a thin porous film with high surface area to volume ratio. Due to these unique characteristics, it is widely used for many application fields such as photocatalyst, electric sensor, and antibacterial scaffold for tissue engineering. Filtration is one of the main applications of electrospun polymer fibers for specific application of filtering out dust particles and dehumidification. Most polymers which are commonly used in electrospinning are hard to perform the filtering and dehumidification simultaneously because of their low hygroscopic property. To overcome this obstacle, the desiccant polymers are developed such as polyacrylic acid and polysulfobetaine methacrylate. However, the desiccant polymers are generally expensive and need special solvent for electrospinning. An alternating way to solve these problems is mixing desiccant material like zeolite in polymer solution during an electrospinning process. In this study, the free surface energy characteristics of electrospun polyvinylidene fluoride (PVDF) film with various zeolite concentrations are investigated to control the hygroscopic property of general polymers. Fundamental physical property of wettability with PVDF shows hydrophobicity. The electrospun PVDF film with small weight ratio with higher than 0.1% of zeolite powder shows diminished contact angles that certifying the wettability of PVDF can be controlled using desiccant material in electrospinning process. To quantify the surface energy of electrospun PVDF films, sessile water droplets are introduced on the electrospun PVDF film surface and the contact angles are measured. The contact angles of PVDF film are 140° for without zeolite and 80° for with 5 wt% of zeolite respectively. As a result, the surface energy of PVDF film can be controlled by embedding zeolite particles in electrospinning process and applied to filtration application of dust filtering and dehumidification simultaneously with low manufacturing cost.

Microstructured Polymer Blend Surfaces Produced by Spraying Functional Copolymers and Their Blends

PubMed Central

Vargas-Alfredo, Nelson; Rodríguez Hernández, Juan

2016-01-01

We described the fabrication of functional and microstructured surfaces from polymer blends by spray deposition. This simple technique offers the possibility to simultaneously finely tune the microstructure as well as the surface chemical composition. Whereas at lower polymer concentration, randomly distributed surface micropatterns were observed, an increase of the concentration leads to significant changes on these structures. On the one hand, using pure homopolystyrene fiber-like structures were observed when the polymer concentration exceeded 30 mg/mL. Interestingly, the incorporation of 2,3,4,5,6-pentafluorostyrene changed the morphology, and, instead of fibers, micrometer size particles were identified at the surface. These fluorinated microparticles provide superhydrophobic properties leading to surfaces with contact angles above 165°. Equally, in addition to the microstructures provided by the spray deposition, the use of thermoresponsive polymers to fabricate interfaces with responsive properties is also described. Contact angle measurements revealed variations on the surface wettability upon heating when blends of polystyrene and polystyrene-b-poly(dimethylaminoethyl methacrylate) are employed. Finally, the use of spraying techniques to fabricate gradient surfaces is proposed. Maintaining a constant orientation, the surface topography and thus the contact angle varies gradually from the center to the edge of the film depending on the spray angle. PMID:28773555

Effect of plasticizer on surface of free films prepared from aqueous solutions of salts of cationic polymers with different plasticizers

NASA Astrophysics Data System (ADS)

Bajdik, János; Fehér, Máté; Pintye-Hódi, Klára

2007-06-01

Acquisition of a more detailed understanding of all technological processes is currently a relevant tendency in pharmaceutical technology and hence in industry. A knowledge of film formation from dispersion of polymers is very important during the coating of solid dosage forms. This process and the structure of the film can be influenced by different additives. In the present study, taste-masking films were prepared from aqueous citric acid solutions of a cationic polymer (Eudragit ® E PO) with various hydrophilic plasticizers (glycerol, propylene glycol and different poly(ethylene glycols)). The mechanical properties, film thickness, wetting properties and surface free energy of the free films were studied. The aim was to evaluate the properties of surface of free films to predict the arrangement of macromolecules in films formed from aqueous solutions of salts of cationic polymers. A high molecular weight of the plasticizer decreased the work of deformation. The surface free energy and the polarity were highest for the film without plasticizer; the hydrophilic additives decreased these parameters. The direction of the change in polarity (a hydrophilic component caused a decrease in the polarity) was unexpected. It can be explained by the change in orientation of the macromolecules, a hydrophobic surface being formed. Examination of the mechanical properties and film thickness can furnish additional results towards a knowledge of film formation by this not frequently applied type of polymer from aqueous solution.

Fate of Eight Different Polymers under Uncontrolled Composting Conditions: Relationships Between Deterioration, Biofilm Formation, and the Material Surface Properties.

PubMed

Mercier, Anne; Gravouil, Kevin; Aucher, Willy; Brosset-Vincent, Sandra; Kadri, Linette; Colas, Jenny; Bouchon, Didier; Ferreira, Thierry

2017-02-21

With the ever-increasing volume of polymer wastes and their associated detrimental impacts on the environment, the plastic life cycle has drawn increasing attention. Here, eight commercial polymers selected from biodegradable to environmentally persistent materials, all formulated under a credit card format, were incubated in an outdoor compost to evaluate their fate over time and to profile the microbial communities colonizing their surfaces. After 450 days in compost, the samples were all colonized by multispecies biofilms, these latest displaying different amounts of adhered microbial biomass and significantly distinct bacterial and fungal community compositions depending on the substrate. Interestingly, colonization experiments on the eight polymers revealed a large core of shared microbial taxa, predominantly composed of microorganisms previously reported from environments contaminated with petroleum hydrocarbons or plastics debris. These observations suggest that biofilms may contribute to the alteration process of all the polymers studied. Actually, four substrates, independently of their assignment to a polymer group, displayed a significant deterioration, which might be attributed to biologically mediated mechanisms. Relevantly, the deterioration appears strongly associated with the formation of a high-cell density biofilm onto the polymer surfaces. The analysis of various surface properties revealed that roughness and hydrophilicity are likely prominent parameters for driving the biological interactions with the polymers.

Ordered polymer nanofibers enhance output brightness in bilayer light-emitting field-effect transistors.

PubMed

Hsu, Ben B Y; Seifter, Jason; Takacs, Christopher J; Zhong, Chengmei; Tseng, Hsin-Rong; Samuel, Ifor D W; Namdas, Ebinazar B; Bazan, Guillermo C; Huang, Fei; Cao, Yong; Heeger, Alan J

2013-03-26

Polymer light emitting field effect transistors are a class of light emitting devices that reveal interesting device physics. Device performance can be directly correlated to the most fundamental polymer science. Control over surface properties of the transistor dielectric can dramatically change the polymer morphology, introducing ordered phase. Electronic properties such as carrier mobility and injection efficiency on the interface can be promoted by ordered nanofibers in the polymer. Moreover, by controlling space charge in the polymer interface, the recombination zone can be spatially extended and thereby enhance the optical output.

Structure-Property Relationships of Polymer Brushes in Restricted Geometries and their Utilization as Ultra-Low Lubricants

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

Kuhl, Tonya Lynn; Faller, Roland

2015-09-28

Though polymer films are widely used to modify or tailor the physical, chemical and mechanical properties of interfaces in both solid and liquid systems, the rational design of interface- or surface-active polymer modifiers has been hampered by a lack of information about the behavior and structure-property relationships of this class of molecules. This is especially true for systems in which the role of the polymer is to modify the interaction between two solid surfaces in intimate contact and under load, to cause them to be mechanically coupled (e.g. to promote adhesion and wetting) or to minimize their interaction (e.g. lubrication,more » colloidal stabilization, etc.). Detailed structural information on these systems has largely been precluded by the many difficulties and challenges associated with direct experimental measurements of polymer structure in these geometries. As a result, many practitioners have been forced to employ indirect measurements or rely wholly on theoretical modeling. This has resulted in an incomplete understanding of the structure-property relationships, which are relied upon for the rational design of improved polymer modifiers. Over the course of this current research program, we made direct measurements of the structure of polymers at the interface between two solid surfaces under confinement and elucidated the fundamental physics behind these phenomena using atomistic and coarse grained simulations. The research has potential to lead to new lubricants and wear reducing agents to improve efficiency.« less

Polymer-Nanoparticle Composites: From Synthesis to Modern Applications

PubMed Central

Hanemann, Thomas; Szabó, Dorothée Vinga

2010-01-01

The addition of inorganic spherical nanoparticles to polymers allows the modification of the polymers physical properties as well as the implementation of new features in the polymer matrix. This review article covers considerations on special features of inorganic nanoparticles, the most important synthesis methods for ceramic nanoparticles and nanocomposites, nanoparticle surface modification, and composite formation, including drawbacks. Classical nanocomposite properties, as thermomechanical, dielectric, conductive, magnetic, as well as optical properties, will be summarized. Finally, typical existing and potential applications will be shown with the focus on new and innovative applications, like in energy storage systems.

Polymer Nanocomposites: Insights from Theory and Molecular Simulations

NASA Astrophysics Data System (ADS)

Pani, Rakhee

Advantages of polymer nanocomposites have attracted great industrial attention due to their multifunctionality and innovative technological properties. Addition of small amount of nanoparticle (nanospheres, nanotubes, nanorods, nanoplatelets, or sheets) to polymer matrix cause dramatic improvement in structural and functional properties, which is difficult to attain from those of individual components. The interaction between polymer and nanoparticle create bulk materials dominated by solid state physics at the nanoscale. Furthermore, morphology of nanocomposites depends on structural arrangements of nanoparticles. Thus, for achievement of optimized functionality like electrical, optical, mechanical and thermal properties control over the dispersion of the nanoparticle is essential. However, properties of polymer nanocomposites depend on morphology control and nature of interfacial interactions. In order to control the morphology it is necessary to understand how the processing conditions, shape and size of nanoparticle influence the structure of composite. Molecular simulations can help us to predict the parameters that control the structural changes and we could design polymer nanocomposite entailing their end-use. In this work, we addressed the following research questions: (1) the dependence of nanoparticle ligand corona structure on solvent quality and (2) the role of interfacial energy and interactions on the dispersion of molecules and nanoparticles. Specifically, this research assessed the effect of solvent interactions on the structure of nanoparticles on the example of redox core encapsulating dendrimer and ligand functionalized gold nanoparticles, role of chemical interaction on solubility of glucose in ionic liquids, diffusion of fullerene nanoparticles in polymer matrix and influence of solubility parameters on the compatibility of gold nanoparticles with diblock copolymers. Computational methods allow quantifying the structure and flexibility of the polymer chains, how energetics and surface tension change with chemical composition of the polymer/dendrimer blocks, influence of nanoparticle on structural properties of polymer and factors which may contribute to the phase separation of the polymer from nanoparticle. Interfacial characteristics are not only determined by the size-induced properties, but also the surface chemistry of the particles. Presence of solvent and the resultant interactions with the solvent are known to influence the morphology and prevent or induce aggregation of nanoparticles in polymers. We found that surface chemistry can induce change in the structure of dendrimers encapsulating a redox active core and change the solubility of the nanoparticles. The interactions between nanoparticles and polymers can also influence the morphology. We performed investigation on the role of orientation of fullerene derivatives and surface energy of polymer surface which may induce the aggregation of the fullerene nanoparticles. Furthermore, we used quantitative measurements like cluster analysis to understand the most probable orientation of the fullerene derivative with respect to the polymer chains and the diffusion of the fullerene nanoparticle, which is related to the efficiency of solar cells, can change on presence of regiorandom and regioregular polymer chains. Furthermore, we have also used different solvents based on their Hildebrand solubility parameters to investigate factors governing the morphology of polymer nanocomposite via solvent interactions. We showed that change in solvent interactions affect the compatibility, aggregation/dispersion of the gold nanoparticles, which will directly affect the morphology of polymer matrix and structural aspects which can impact their functionality. Overall, our research indicated that solvent interaction play a role in controlling the morphology of polymer nanocomposite and solubility parameter can help us to predict the resulting morphology.

Texturing of UHMWPE surface via NIL for low friction and wear properties

NASA Astrophysics Data System (ADS)

Suryadi Kustandi, Tanu; Choo, Jian Huei; Low, Hong Yee; Sinha, Sujeet K.

2010-01-01

Wear is a major obstacle limiting the useful life of implanted ultra-high molecular weight polyethylene (UHMWPE) components in total joint arthroplasty. It has been a continuous effort in the implant industry to reduce the frictional wear problem of UHMWPE by improving the structure, morphology and mechanical properties of the polymer. In this paper, a new paradigm that utilizes nanoimprint lithography (NIL) in producing textures on the surface of UHMWPE is proposed to efficiently improve the tribological properties of the polymer. Friction and wear experiments were conducted on patterned and controlled (non-patterned) UHMWPE surfaces using a commercial tribometer, mounted with a silicon nitride ball, under a dry-sliding condition with normal loads ranging from 60 to 200 mN. It has been shown that the patterned UHMWPE surface showed a reduction in the coefficient of friction between 8% and 35% as compared with the controlled (non-patterned) surface, depending on the magnitude of the normal load. Reciprocating wear experiments also showed that the presence of surface textures on the polymer resulted in lower wear depth and width, with minimal material transfer to the sliding surface.

Effects of anisotropic surface texture on the performance of ionic polymer-metal composite (IPMC)

NASA Astrophysics Data System (ADS)

He, Qingsong; Yu, Min; Ding, Haitao; Guo, Dongjie; Dai, Zhendong

2010-04-01

Ionic polymer metal composite (IPMC), an electrically activated polymer (EAP), has attracted great attention for the excellent properties such as large deformation, light weight, low noise, flexibility and low driving voltages, which makes the material a possible application as artificial muscle if the output force can be increased. To improve the property, we manufactured the Nafion membrane by casting from liquid solution, modified the surface by sandblasting or polishing, and obtained the isotropic and anisotropic surface texture respectively. The microstructure of the Nafion surface and metal electrode, effects of surface texture on the output force and displacement of IPMC were studied. Results show that the output force of IPMC with the anisotropic surface texture is 2~4 times higher than that with the isotropic surface texture without enormous sacrifice of the displacement. The output force may reach to 6.63gf (Sinusoidal 3.5V and 0.1Hz, length 20mm, width 5mm and thickness 0.66mm), which suggest an effective way to improve the mechanical properties of IPMC.

Nanomechanics of cellulose crystals and cellulose-based polymer composites

NASA Astrophysics Data System (ADS)

Pakzad, Anahita

Cellulose-polymer composites have potential applications in aerospace and transportation areas where lightweight materials with high mechanical properties are needed. In addition, these economical and biodegradable composites have been shown to be useful as polymer electrolytes, packaging structures, optoelectronic devices, and medical implants such as wound dressing and bone scaffolds. In spite of the above mentioned advantages and potential applications, due to the difficulties associated with synthesis and processing techniques, application of cellulose crystals (micro and nano sized) for preparation of new composite systems is limited. Cellulose is hydrophilic and polar as opposed to most of common thermoplastics, which are non-polar. This results in complications in addition of cellulose crystals to polymer matrices, and as a result in achieving sufficient dispersion levels, which directly affects the mechanical properties of the composites. As in other composite materials, the properties of cellulose-polymer composites depend on the volume fraction and the properties of individual phases (the reinforcement and the polymer matrix), the dispersion quality of the reinforcement through the matrix and the interaction between CNCs themselves and CNC and the matrix (interphase). In order to develop economical cellulose-polymer composites with superior qualities, the properties of individual cellulose crystals, as well as the effect of dispersion of reinforcements and the interphase on the properties of the final composites should be understood. In this research, the mechanical properties of CNC polymer composites were characterized at the macro and nano scales. A direct correlation was made between: - Dispersion quality and macro-mechanical properties - Nanomechanical properties at the surface and tensile properties - CNC diameter and interphase thickness. Lastly, individual CNCs from different sources were characterized and for the first time size-scale effect on their nanomechanical properties were reported. Then the effect of CNC surface modification on the mechanical properties was studied and correlated to the crystalline structure of these materials.

Poly(ethylene oxide) surfactant polymers.

PubMed

Vacheethasanee, Katanchalee; Wang, Shuwu; Qiu, Yongxing; Marchant, Roger E

2004-01-01

We report on a series of structurally well-defined surfactant polymers that undergo surface-induced self-assembly on hydrophobic biomaterial surfaces. The surfactant polymers consist of a poly(vinyl amine) backbone with poly(ethylene oxide) and hexanal pendant groups. The poly(vinyl amine) (PVAm) was synthesized by hydrolysis of poly(N-vinyl formamide) following free radical polymerization of N-vinyl formamide. Hexanal and aldehyde-terminated poly(ethylene oxide) (PEO) were simultaneously attached to PVAm via reductive amination. Surfactant polymers with different PEO:hexanal ratios and hydrophilic/hydrophobic balances were prepared, and characterized by FT-IR, 1H-NMR and XPS spectroscopies. Surface active properties at the air/water interface were determined by surface tension measurements. Surface activity at a solid surface/water interface was demonstrated by atomic force microscopy, showing epitaxially molecular alignment for surfactant polymers adsorbed on highly oriented pyrolytic graphite. The surfactant polymers described in this report can be adapted for simple non-covalent surface modification of biomaterials and hydrophobic surfaces to provide highly hydrated interfaces.

UV light induced surface modification of HDPE films with bioactive compounds

NASA Astrophysics Data System (ADS)

Daniloska, Vesna; Blazevska-Gilev, Jadranka; Dimova, Vesna; Fajgar, Radek; Tomovska, Radmila

2010-01-01

The development of different techniques for surface modification of polymers becomes popular in a last decade. These techniques preserve useful bulk polymer properties unchanged, while the activation of the polymer surface offers more possibilities for polymer applications. In this work, a new, one-step method for bio-activation of HDPE (high density polyethylene) surface by UV irradiation is presented. HDPE films coupled with selected active compound and a photoinitiator was treated by UV lamp, emitting light at 254 nm. For surface functionalization of HDPE films, the following compounds were employed: 2-aminopyridine (AP), N 1-(2-pyridylaminomethyl)-1,2,4-triazole (TA) and benzocaine (BC). The influence of irradiation time on the extent of surface changes was investigated. The modified polymer surfaces were investigated by Fourier transformed infrared (FTIR) and Raman spectroscopy, scanning electron microscopy (SEM) and contact angle measurements, demonstrating successful functionalization of HDPE surface.

Formation and properties of surface-anchored polymer assemblies with tunable physico-chemical characteristics

NASA Astrophysics Data System (ADS)

Wu, Tao

We describe two new methodologies leading to the formation of novel surface-anchored polymer assemblies on solid substrates. While the main goal is to understand the fundamentals pertaining to the preparation and properties of the surface-bound polymer assemblies (including neutral and chargeable polymers), several examples also are mentioned throughout the Thesis that point out to practical applications of such structures. The first method is based on generating assemblies comprising anchored polymers with a gradual variation of grafting densities on solid substrates. These structures are prepared by first covering the substrate with a molecular gradient of the polymerization initiator, followed by polymerization from these substrate-bound initiator centers ("grafting from"). We apply this technique to prepare grafting density gradients of poly(acryl amide) (PAAm) and poly(acrylic acid) (PAA) on silica-covered substrates. We show that using the grafting density gradient geometry, the characteristics of surface-anchored polymers in both the low grafting density ("mushroom") regime as well as the high grafting density ("brush") regime can be accessed conveniently on a single sample. We use a battery of experimental methods, including Fourier transform infrared spectroscopy (FTIR), Near-edge absorption fine structure spectroscopy (NEXAFS), contact angle, ellipsometry, to study the characteristics of the surface-bound polymer layers. We also probe the scaling laws of neutral polymer as a function of grafting density, and for weak polyelectrolyte, in addition to the grafting density, we study the affect of solution ionic strength and pH values. In the second novel method, which we coined as "mechanically assisted polymer assembly" (MAPA), we form surface anchored polymers by "grafting from" polymerization initiators deposited on elastic surfaces that have been previously extended uniaxially by a certain length increment, Deltax. Upon releasing the strain in the substrate after completion of polymerization, we show the grafting density of the polymers grafted to flexible substrates can be tuned as a function of Deltax.

Role of Monomer Sequence, Hydrogen Bonding and Mesoscale Architecture in Marine Antifouling Coatings

NASA Astrophysics Data System (ADS)

Segalman, Rachel

Polypeptoids are non-natural, sequence specific polymers that offer the opportunity to probe the effect of monomer sequence, chirality, and chain shape on self-assembly and surface properties. Additionally, polypeptoid synthesis is more scaleable than traditional polypeptides suggesting their utility in large area applications. We have designed efficient marine anti-fouling coatings by using triblock copolymer scaffolds to which polypeptoids are tethered in order to tune both the modulus and surface energies with great precision. Surprisingly, when short sequences are tethered to a polymer backbone, polypeptoids consistently outperform analogous polypeptides in antifouling properties. We hypothesize that the hydrogen bonding inherent to the polypeptide backbone drives the observed differences in performance. We also find that the polymer scaffold housing the polypeptoids also plays a crucial role in directing surface presentation and therefore the overall coating properties.

Functionalization of silicon nanowires by conductive and non-conductive polymers

NASA Astrophysics Data System (ADS)

Belhousse, S.; Tighilt, F.-Z.; Sam, S.; Lasmi, K.; Hamdani, K.; Tahanout, L.; Megherbi, F.; Gabouze, N.

2017-11-01

The work reports on the development of hybrid devices based on silicon nanowires (SiNW) with polymers and the difference obtained when using conductive and non-conductive polymers. SiNW have attracted much attention due to their importance in understanding the fundamental properties at low dimensionality as well as their potential application in nanoscale devices as in field effect transistors, chemical or biological sensors, battery electrodes and photovoltaics. SiNW arrays were formed using metal assisted chemical etching method. This process is simple, fast and allows obtaining a wide range of silicon nanostructures. Hydrogen-passivated SiNW surfaces show relatively poor stability. Surface modification with organic species confers the desired stability and enhances the surface properties. For this reason, this work proposes a covalent grafting of organic material onto SiNW surface. We have chosen a non-conductive polymer polyvinylpyrrolidone (PVP) and conductive polymers polythiophene (PTh) and polypyrrole (PPy), in order to evaluate the electric effect of the polymers on the obtained materials. The hybrid structures were elaborated by the polymerization of the corresponding conjugated monomers by electrochemical route; this electropolymerization offers several advantages such as simplicity and rapidity. SiNW functionalization by conductive polymers has shown to have a huge effect on the electrical mobility. Hybrid surface morphologies were characterized by scanning electron microscopy (SEM), infrared spectroscopy (FTIR-ATR) and contact angle measurements.

Material properties of novel polymeric films

NASA Astrophysics Data System (ADS)

Kim, Gene

This dissertation will study the material properties of two types of novel polymer films (polyelectrolyte multilayer films and photolithographic polymer films). The formation of polylelectrolyte multilayer films onto functionalized aluminum oxide surfaces and functionalized poly(ethylene terephthaltate) (PET) were studied. Functionalization of the aluminum oxide surfaces was achieved via silane coupling. Functionalization of PET surfaces was achieved via hydrolysis and amidation. Surface characterization techniques such as X-ray photoelectron spectroscopy (XPS) and dynamic contact angle measurements were used to monitor the polyelectrolyte multilayer formation. Mechanical properties of the aluminum oxide supported polyelectrolyte multilayer films were tested using a simplified peel test. XPS was used to analyze the surfaces before and after peel. Single lap shear joint specimens were constructed to test the adhesive shear strength of the PET-supported polyelectrolyte multilayer film samples with the aid of a cyanoacrylate adhesive. The adhesive shear strength and its relation with the type of functionalization, number of polyelectrolyte layers, and the effect of polyelectrolyte conformation using added salt were explored. Also, characterization on the single lap joints after adhesive failure was carried out to determine the locus of failure within the multilayers by using XPS and SEM. Two types of photolithographic polymers were formulated and tested. These two polymers (photocrosslinkable polyacrylate (PUA), and a photocrosslinkable polyimide (HRP)) were used to investigate factors that would affect the structural integrity of these particular polymers under environmental variables such as processing (time, UV cure, pressure, and temperature) and ink exposure. Thermomechanical characterization was carried out to see the behavior of these two polymers under these environmental variables. Microscopic techniques were employed to study the morphological behavior of the two polymer systems. Also, unique in-house characterization methods such as the vibrational holographic interferometry to measure residual stress in these polymer coatings upon processing, and the environmental tensile tester (ETT) to measure ink diffusion and swelling stresses were used to further characterize these two polymers.

Fracture surface analysis in composite and titanium bonding

NASA Technical Reports Server (NTRS)

Devilbiss, T. A.; Wightman, J. P.

1985-01-01

To understand the mechanical properties of fiber-reinforced composite materials, it is necessary to understand the mechanical properties of the matrix materials and of the reinforcing fibers. Another factor that can affect the mechanical properties of a composite material is the interaction between the fiber and the matrix. In general, composites with strong fiber matrix bonding will give higher modulus, lower toughness composites. Composites with weak bonding will have a lower modulus and more ductility. The situation becomes a bit more complex when all possibilities are examined. To be considered are the following: the properties of the surface layer on the fiber, the interactive forces between polymer and matrix, the surface roughness and porosity of the fiber, and the morphology of the matrix polymer at the fiber surface. In practice, the surface of the fibers is treated to enhance the mechanical properties of a composite. These treatments include anodization, acid etching, high temperature oxidation, and plasma oxidation, to name a few. The goal is to be able to predict the surface properties of carbon fibers treated in various ways, and then to relate surface properties to fiber matrix bonding.

Effects of Surface Roughness and Mechanical Properties of Cover-Layer on Near-Field Optical Recording

NASA Astrophysics Data System (ADS)

Kim, Jin-Hong; Lee, Jun-Seok; Lim, Jungshik; Seo, Jung-Kyo

2009-03-01

Narrow gap distance in cover-layer incident near-field recording (NFR) configuration causes a collision problem in the interface between a solid immersion lens and a disk surface. A polymer cover-layer with smooth surface results in a stable gap servo while a nanocomposite cover-layer with high refractive index shows a collision problem during the gap servo test. Even though a dielectric cover-layer, in which the surface is rougher than the polymer, supplements the mechanical properties, an unclear eye pattern due to an unstable gap servo can be obtained after a chemical mechanical polishing. Not only smooth surface but also good mechanical properties of cover-layer are required for the stable gap servo in the NFR.

Sialic acid-triggered macroscopic properties switching on a smart polymer surface

NASA Astrophysics Data System (ADS)

Xiong, Yuting; Li, Minmin; Wang, Hongxi; Qing, Guangyan; Sun, Taolei

2018-01-01

Constructing smart surfaces with responsive polymers capable of dynamically and reversibly changing their chemical and physical properties by responding to the recognition of biomolecules remains a challenging task. And, the key to achieving this purpose relies on the design of polymers to precisely interact with the target molecule and successfully transform the interaction signal into tunable macroscopic properties, further achieve special bio-functions. Herein, inspired by carbohydrate-carbohydrate interaction (CCI) in life system, we developed a three-component copolymer poly(NIPAAm-co-PT-co-Glc) bearing a binding unit glucose (Glc) capable of recognizing sialic acid, a type of important molecular targets for cancer diagnosis and therapy, and reported the sialic acid triggered macroscopic properties switching on this smart polymer surface. Detailed mechanism studies indicated that multiple hydrogen bonding interactions between Glc unit and Neu5Ac destroyed the initial hydrogen bond network of the copolymer, leading to a reversible "contraction-to-swelling" conformational transition of the copolymer chains, accompanied with distinct macroscopic property switching (i.e., surface wettability, morphology, stiffness) of the copolymer film. And these features enabled this copolymer to selectively capture sialic acid-containing glycopeptides from complex protein samples. This work provides an inspiration for the design of novel smart polymeric materials with sensitive responsiveness to sialic acid, which would promote the development of sialic acid-specific bio-devices and drug delivery systems.

Differential partition of virulent Aeromonas salmonicida and attenuated derivatives possessing specific cell surface alterations in polymer aqueous-phase systems

NASA Technical Reports Server (NTRS)

Van Alstine, J. M.; Trust, T. J.; Brooks, D. E.

1986-01-01

Two-polymer aqueous-phase systems in which partitioning of biological matter between the phases occurs according to surface properties such as hydrophobicity, charge, and lipid composition are used to compare the surface properties of strains of the fish pathogen Aeromonas salmonicida. The differential ability of strains to produce a surface protein array crucial to their virulence, the A layer, and to produce smooth lipopolysaccharide is found to be important in the partitioning behavior of Aeromonas salmonicida. The presence of the A layer is shown to decrease the surface hydrophilicity of the pathogen, and to increase specifically its surface affinity for fatty acid esters of polyethylene glycol. The method has application to the analysis of surface properties crucial to bacterial virulence, and to the selection of strains and mutants with specific surface characteristics.

Atmospheric-Pressure Plasma Jet Surface Treatment for Use in Improving Adhesion

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

Kuettner, Lindsey Ann

Atmospheric-pressure plasma jets (APPJs) are a method of plasma treatment that plays an important role in material processing and modifying surface properties of materials, especially polymers. Gas plasmas react with polymer surfaces in numerous ways such as oxidation, radical formation, degradation, and promotion of cross-linking. Because of this, gas and plasma conditions can be explored for chosen processes to maximize desired properties. The purpose of this study is to investigate plasma parameters in order to modify surface properties for improved adhesion between aluminum and epoxy substrates using two types of adhesives. The background, results to date, and future work willmore » be discussed.« less

Interactions of polymer surfaces and thin films

NASA Astrophysics Data System (ADS)

Zeng, Hongbo

2007-12-01

Characterization of the adhesion, tribological properties and dynamics of polymer surfaces has been of great interest for many years since polymers are commonly used as adhesive and lubricant coatings to produce both high and low adhesion or friction. Improving our fundamental understanding of the interactions of polymer surfaces at the molecular level is needed to develop further techniques in materials science and chemical engineering. The objectives of my research were to correlate the nano- and micro-scale properties of various polymer thin film and surface phenomena: adhesion, adhesion hysteresis, friction, lubrication, surface deformations, coalescence, spreading, and wear, and identify the fundamental physical forces and mechanisms at the molecular and micro-scales. I studied the adhesion of polymer films at temperatures ranging from below to above the glass transition temperature, Tg. The adhesion hysteresis was found to peak somewhere around Tg, but to also depend on the load, contact time and detachment rate. The results revealed some new scaling relations for the dynamic (rate-dependent) adhesion forces and effective surface energies of polymers. I studied the way polymer surfaces deform during adhesion (coalescence), spreading (wetting) and separation (detachment, rupture, fracture and failure) processes, and characterized the differences (and transition) between liquid-like and solid-like behavior during these processes, e.g., the transition from liquid-to-viscoelastic-to-ductile-to-brittle behavior. Complex and novel transient (dynamic) surface shape changes were found to occur during transitions that involved highly-ordered or disordered fingers, ripples, waves or cracks. A full picture has emerged for the transition from viscous liquid-like to brittle solid-like behavior of adhering and detaching interfaces. Finally, I developed a new experiment technique whereby an electric field can be applied across the two surfaces in a Surface Force Apparatus for the first time, and two types of experiments were performed to measure the normal and/or lateral forces between two surfaces under an E-field.

Characterization of novel soybean-oil-based thermosensitive amphiphilic polymers for drug delivery applications

USDA-ARS?s Scientific Manuscript database

Characterization, aggregation behavior, physical properties and drug-polymer interaction of novel soybean oil-based polymers i.e., hydrolyzed polymers of (epoxidized) soybean oil (HPESO), were studied. The surface tension method was used to determine the critical micelle concentration (CMC). CMC w...

Functional patterned coatings by thin polymer film dewetting.

PubMed

Telford, Andrew M; Thickett, Stuart C; Neto, Chiara

2017-12-01

An approach for the fabrication of functional polymer surface coatings is introduced, where micro-scale structure and surface functionality are obtained by means of self-assembly mechanisms. We illustrate two main applications of micro-patterned polymer surfaces obtained through dewetting of bilayers of thin polymer films. By tuning the physical and chemical properties of the polymer bilayers, micro-patterned surface coatings could be produced that have applications both for the selective attachment and patterning of proteins and cells, with potential applications as biomaterials, and for the collection of water from the atmosphere. In all cases, the aim is to achieve functional coatings using approaches that are simple to realize, use low cost materials and are potentially scalable. Copyright © 2017 Elsevier Inc. All rights reserved.

From neutral to zwitterionic poly(α-amino acid) nonfouling surfaces: Effects of helical conformation and anchoring orientation.

PubMed

Zhang, Chong; Yuan, Jingsong; Lu, Jianhua; Hou, Yingqin; Xiong, Wei; Lu, Hua

2018-02-03

The development of high-performance nonfouling polymer surfaces for implantable medical devices and therapeutic nanomaterials is of great importance. Elaborating the relationship of polymer structural characteristics and the resulted surface properties can offer useful guidance toward ideal biointerfaces. In this work, we investigate the effects of the helical conformation and anchoring orientation of poly(α-amino acid)s (PαAAs) to produce advanced nonfouling surfaces. By using the neutral poly(γ-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)esteryl glutamates) (P(EG 3 Glu)s) as a model system, the adsorption kinetics are monitored by ex-situ variable angle spectroscopic ellipsometry and in-situ quartz crystal microbalance with dissipation. It is found that the polymers adopting a rigid rod-like α-helical conformation can self-assemble more rapidly to produce denser adlayers, and generate significantly improved nonfouling surfaces compared to those flexible polymer analogues including the widely used antifouling polymer PEG. Moreover, the surface properties can be further enhanced by using the antiparallel orientated helical P(EG 3 Glu)s. Most importantly, the insights gained from the P(EG 3 Glu) model system are successfully applied to the generation of ultra-low-fouling surfaces using zwitterionic PαAAs brushes, underscoring the generality of the approach. Particularly, the surface based on the antiparallel aligned zwitterionic helical PαAAs exhibits ∼98-99% reduction of human serum adsorption relative to the bare gold, and gives almost no adhesion of mouse platelet. Taken together, this work depicts an extremely simple yet highly effective approach to manipulate surface properties for numerous applications in biomaterial interfaces, diagnostics, and biosensors. Copyright © 2018 Elsevier Ltd. All rights reserved.

NASA Astrophysics Data System (ADS)

Cheraghian, Goshtasp; Khalili Nezhad, Seyyed Shahram; Kamari, Mosayyeb; Hemmati, Mahmood; Masihi, Mohsen; Bazgir, Saeed

2014-07-01

Nanotechnology has been used in many applications and new possibilities are discovered constantly. Recently, a renewed interest has risen in the application of nanotechnology for the upstream petroleum industry, such as exploration, drilling, production and distribution. In particular, adding nanoparticles to fluids may significantly benefit enhanced oil recovery and improve well drilling, such as changing the properties of the fluid, wettability alternation of rocks, advanced drag reduction, strengthening sand consolidation, reducing the interfacial tension and increasing the mobility of the capillary-trapped oil. In this study, we focus on the roles of clay and silica nanoparticles in adsorption process on reservoir rocks. Polymer-flooding schemes for recovering residual oil have been in general less satisfactory due to loss of chemicals by adsorption on reservoir rocks, precipitation, and resultant changes in rheological properties. Adsorption and rheological property changes are mainly determined by the chemical structure of the polymers, surface properties of the rock, composition of the oil and reservoir fluids, the nature of the polymers added and solution conditions such as salinity, pH and temperature. Because this method relies on the adsorption of a polymer layer onto the rock surface, a deeper understanding of the relevant polymer-rock interactions is of primary importance to develop reliable chemical selection rules for field applications. In this paper, the role of nanoparticles in the adsorption of water-soluble polymers onto solid surfaces of carbonate and sandstone is studied. The results obtained by means of static adsorption tests show that the adsorption is dominated by the nanoclay and nanosilica between the polymer molecules and the solid surface. These results also show that lithology, brine concentration and polymer viscosity are critical parameters influencing the adsorption behavior at a rock interface. On the other hand, in this study, the focus is on viscosity, temperature and salinity of solutions of polyacrylamide polymers with different nanoparticle degrees and molecular weight. The adsorption of nanopolymer solution is always higher in carbonated stones than in sandstones, and polymer solutions containing silica nanoparticles have less adsorption based on weight percent than similar samples containing clay. Based on the area of contact for stone, this behavior is the same regarding adsorption.

Modification of anti-bacterial surface properties of textile polymers by vacuum arc ion source implantation

NASA Astrophysics Data System (ADS)

Nikolaev, A. G.; Yushkov, G. Yu.; Oks, E. M.; Oztarhan, A.; Akpek, A.; Hames-Kocabas, E.; Urkac, E. S.; Brown, I. G.

2014-08-01

Ion implantation provides an important technology for the modification of material surface properties. The vacuum arc ion source is a unique instrument for the generation of intense beams of metal ions as well as gaseous ions, including mixed metal-gas beams with controllable metal:gas ion ratio. Here we describe our exploratory work on the application of vacuum arc ion source-generated ion beams for ion implantation into polymer textile materials for modification of their biological cell compatibility surface properties. We have investigated two specific aspects of cell compatibility: (i) enhancement of the antibacterial characteristics (we chose to use Staphylococcus aureus bacteria) of ion implanted polymer textile fabric, and (ii) the "inverse" concern of enhancement of neural cell growth rate (we chose Rat B-35 neuroblastoma cells) on ion implanted polymer textile. The results of both investigations were positive, with implantation-generated antibacterial efficiency factor up to about 90%, fully comparable to alternative conventional (non-implantation) approaches and with some potentially important advantages over the conventional approach; and with enhancement of neural cell growth rate of up to a factor of 3.5 when grown on suitably implanted polymer textile material.

The selectivity of protein-imprinted gels and its relation to protein properties: A computer simulation study.

PubMed

Yankelov, Rami; Yungerman, Irena; Srebnik, Simcha

2017-07-01

Polymer-based protein recognition systems have enormous potential within clinical and diagnostic fields due to their reusability, biocompatibility, ease of manufacturing, and potential specificity. Imprinted polymer matrices have been extensively studied and applied as a simple technique for creating artificial polymer-based recognition gels for a target molecule. Although this technique has been proven effective when targeting small molecules (such as drugs), imprinting of proteins have so far resulted in materials with limited selectivity due to the large molecular size of the protein and aqueous environment. Using coarse-grained molecular simulation, we investigate the relation between protein makeup, polymer properties, and the selectivity of imprinted gels. Nonspecific binding that results in poor selectivity is shown to be strongly dependent on surface chemistry of the template and competitor proteins as well as on polymer chemistry. Residence time distributions of proteins diffusing within the gels provide a transparent picture of the relation between polymer constitution, protein properties, and the nonspecific interactions with the imprinted gel. The pronounced effect of protein surface chemistry on imprinted gel specificity is demonstrated. Copyright © 2017 John Wiley & Sons, Ltd.

Polymethyl methacrylate-co-methacrylic acid coatings with controllable concentration of surface carboxyl groups: A novel approach in fabrication of polymeric platforms for potential bio-diagnostic devices

NASA Astrophysics Data System (ADS)

Hosseini, Samira; Ibrahim, Fatimah; Djordjevic, Ivan; Koole, Leo H.

2014-05-01

The generally accepted strategy in development of bio-diagnostic devices is to immobilize proteins on polymeric surfaces as a part of detection process for diseases and viruses through antibody/antigen coupling. In that perspective, polymer surface properties such as concentration of functional groups must be closely controlled in order to preserve the protein activity. In order to improve the surface characteristics of transparent polymethacrylate plastics that are used for diagnostic devices, we have developed an effective fabrication procedure of polymethylmetacrylate-co-metacrylic acid (PMMA-co-MAA) coatings with controlled number of surface carboxyl groups. The polymers were processed effectively with the spin-coating technique and the detailed control over surface properties is here by demonstrated through the variation of a single synthesis reaction parameter. The chemical structure of synthesized and processed co-polymers has been investigated with nuclear magnetic resonance spectroscopy (NMR) and matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-ToF-MS). The surface morphology of polymer coatings have been analyzed with atomic force microscopy (AFM) and scanning electron microscopy (SEM). We demonstrate that the surface morphology and the concentration of surface -COOH groups (determined with UV-vis surface titration) on the processed PMMA-co-MAA coatings can be precisely controlled by variation of initial molar ratio of reactants in the free-radical polymerization reaction. The wettability of developed polymer surfaces also varies with macromolecular structure.

Influence of Polymers on the Crystal Growth Rate of Felodipine: Correlating Adsorbed Polymer Surface Coverage to Solution Crystal Growth Inhibition.

PubMed

Schram, Caitlin J; Taylor, Lynne S; Beaudoin, Stephen P

2015-10-20

The bioavailability of orally administered drugs that exhibit poor aqueous solubility can be enhanced with the use of supersaturating dosage forms. Stabilization of these forms by preventing or inhibiting crystallization in solution is an important area of study. Polymers can be used to stabilize supersaturated systems; however, the properties that impact their effectiveness as crystal growth rate inhibitors are not yet fully understood. In this study, the impact of various polymers on the crystal growth rate of felodipine and the conformation of these polymers adsorbed to crystalline felodipine was investigated in order to gain a mechanistic understanding of crystal growth inhibition. It was determined that polymer hydrophobicity impacted polymer adsorption as well as adsorbed polymer conformation. Polymer conformation impacts its surface coverage, which was shown to directly correlate to the polymer's effectiveness as a growth rate inhibitor. By modeling this correlation, it is possible to predict polymer effectiveness given the surface coverage of the polymer.

Enhancement in biological response of Ag-nano composite polymer membranes using plasma treatment for fabrication of efficient bio materials

NASA Astrophysics Data System (ADS)

Agrawal, Narendra Kumar; Sharma, Tamanna Kumari; Chauhan, Manish; Agarwal, Ravi; Vijay, Y. K.; Swami, K. C.

2016-05-01

Biomaterials are nonviable material used in medical devices, intended to interact with biological systems, which are becoming necessary for the development of artificial material for biological systems such as artificial skin diaphragm, valves for heart and kidney, lenses for eye etc. Polymers having novel properties like antibacterial, antimicrobial, high adhesion, blood compatibility and wettability are most suitable for synthesis of biomaterial, but all of these properties does not exist in any natural or artificial polymeric material. Nano particles and plasma treatment can offer these properties to the polymers. Hence a new nano-biomaterial has been developed by modifying the surface and chemical properties of Ag nanocomposite polymer membranes (NCPM) by Argon ion plasma treatment. These membranes were characterized using different techniques for surface and chemical modifications occurred. Bacterial adhesion and wettability were also tested for these membranes, to show direct use of this new class of nano-biomaterial for biomedical applications.

Molecular Velcro constructed from polymer loop brushes showing enhanced adhesion force

NASA Astrophysics Data System (ADS)

Zhou, Tian; Han, Biao; Han, Lin; Li, Christopher; Department of Materials Science; Engineering Team; School of Biomedical Engineering, Science; Health Systems Team

2015-03-01

Molecular Velcro is commonly seen in biological systems as the formation of strong physical entanglement at molecular scale could induce strong adhesion, which is crucial to many biological processes. To mimic this structure, we designed, and fabricated polymer loop brushes using polymer single crystals with desired surface functionality and controlled chain folding. Compared with reported loop brushes fabricated using triblock copolymers, the present loop bushes have precise loop sizes, loop grafting density, and well controlled tethering locations on the solid surface. Atomic force microscopy-based force spectroscopy measurements using a polymer chain coated probe reveal that the adhesion force are significantly enhanced on the loop brush surface as compared with its single-strand counterpart. This study directly shows the effect of polymer brush conformation on their properties, and suggests a promising strategy for advanced polymer surface design.

Adhesion properties in systems of laminated pigmented polymers, carbon-graphite fiber composite framework and titanium surfaces in implant suprastructures.

PubMed

Segerström, Susanna; Ruyter, I Eystein

2009-09-01

For long-term stability the adhering interfaces of an implant-retained supraconstruction of titanium/carbon-graphite fiber-reinforced (CGFR) polymer/opaquer layer/denture base polymer/denture teeth must function as a unity. The aim was to evaluate adhesion of CGFR polymer to a titanium surface or CGFR polymer to two different opaquer layers/with two denture base polymers. Titanium plates were surface-treated and silanized and combined with a bolt of CGFR polymer or denture base polymer (Probase Hot). Heat-polymerized plates of CGFR polymer (47 wt% fiber) based on poly(methyl methacrylate) and a copolymer matrix were treated with an opaquer (Sinfony or Ropak) before a denture base polymer bolt was attached (Probase Hot or Lucitone 199). All specimens were heat-polymerized, water saturated (200 days) and thermally cycled (5000 cycles, 5/55 degrees C) before shear bond testing. Silicatized titanium surfaces gave higher bond strength to CGFR polymer (16.2+/-2.34 and 18.6+/-1.32) MPa and cohesive fracture than a sandblasted surface (5.9+/-2.11) MPa where the fracture was adhesive. The opaquer Sinfony gave higher adhesion values and mainly cohesive fractures than the opaquer Ropak. Different surface treatments (roughened or polished) of the CGFR polymer had no effect on bond strength. The fracture surfaces of silicatized titanium/CGFR polymer/opaquer layer (Sinfony)/denture base polymers were mainly cohesive. A combination of these materials in an implant-retained supraconstruction is promising for in vivo evaluation.

Enhancing the biocompatibility of the polyurethane methacrylate and off-stoichiometry thiol-ene polymers by argon and nitrogen plasma treatment.

PubMed

Chen, Tiam Foo; Siow, Kim Shyong; Ng, Pei Yuen; Majlis, Burhanuddin Yeop

2017-10-01

Our studies focused on improving the biocompatibility properties of two microfluidic prototyping substrates i.e. polyurethane methacrylate (PUMA) and off-stoichiometry thiol-ene (OSTE-80) polymer by Ar and N 2 plasma treatment. The contact angle (CA) measurement showed that both plasma treatments inserted oxygen and nitrogen moieties increased the surface energy and hydrophilicity of PUMA and OSTE-80 polymer which corresponded to an increase of nitrogen to carbon ratios (N/C), as measured by XPS, to provide a conducive environment for cell attachments and proliferation. Under the SEM observation, the surface topography of PUMA and OSTE-80 polymer showed minimal changes after the plasma treatments. Furthermore, ageing studies showed that plasma-treated PUMA and OSTE-80 polymer had stable hydrophilicity and nitrogen composition during storage in ambient air for 15days. After in vitro cell culture of human umbilical vein endothelial cells (HUVECs) on these surfaces for 24h and 72h, both trypan blue and alamar blue assays indicated that PUMA and OSTE-80 polymer treated with N 2 plasma had the highest viability and proliferation. The polar nitrogen moieties, specifically amide groups, encouraged the HUVECs adhesion on the plasma-treated PUMA and OSTE-80 surfaces. Interestingly, PUMA polymer treated with Ar and N 2 plasma showed different HUVECs morphology which was spindle and cobblestone-shaped respectively after 72h of incubation. On the contrary, a monolayer of well-spread HUVECs formed on the Ar and N 2 plasma-treated OSTE-80 polymers. These variable morphologies observed can be ascribed to the adherence HUVECs on the different elastic moduli of these surfaces whereby further investigation might be needed. Overall, Ar and N 2 plasma treatment had successfully altered the surface properties of PUMA and OSTE-80 polymer by increasing its surface energy, hydrophilicity and chemical functionalities to create a biocompatible surface for HUVECs adhesion and proliferation. Copyright © 2017 Elsevier B.V. All rights reserved.

Energy storage in ferroelectric polymer nanocomposites filled with core-shell structured polymer@BaTiO3 nanoparticles: understanding the role of polymer shells in the interfacial regions.

PubMed

Zhu, Ming; Huang, Xingyi; Yang, Ke; Zhai, Xing; Zhang, Jun; He, Jinliang; Jiang, Pingkai

2014-11-26

The interfacial region plays a critical role in determining the electrical properties and energy storage density of dielectric polymer nanocomposites. However, we still know a little about the effects of electrical properties of the interfacial regions on the electrical properties and energy storage of dielectric polymer nanocomposites. In this work, three types of core-shell structured polymer@BaTiO3 nanoparticles with polymer shells having different electrical properties were used as fillers to prepare ferroelectric polymer nanocomposites. All the polymer@BaTiO3 nanoparticles were prepared by surface-initiated reversible-addition-fragmentation chain transfer (RAFT) polymerization, and the polymer shells were controlled to have the same thickness. The morphology, crystal structure, frequency-dependent dielectric properties, breakdown strength, leakage currents, energy storage capability, and energy storage efficiency of the polymer nanocomposites were investigated. On the other hand, the pure polymers having the same molecular structure as the shells of polymer@BaTiO3 nanoparticles were also prepared by RAFT polymerization, and their electrical properties were provided. Our results show that, to achieve nanocomposites with high discharged energy density, the core-shell nanoparticle filler should simultaneously have high dielectric constant and low electrical conductivity. On the other hand, the breakdown strength of the polymer@BaTiO3-based nanocomposites is highly affected by the electrical properties of the polymer shells. It is believed that the electrical conductivity of the polymer shells should be as low as possible to achieve nanocomposites with high breakdown strength.

Effect of LEO Exposure on Aromatic Polymers Containing Phenylphosphine Oxide Groups

NASA Technical Reports Server (NTRS)

Lillehei, P. T.; Smith, J. G., Jr.; Connell, J. W.

2008-01-01

As part of the Materials on The International Space Station Experiment (MISSE), aromatic polymers containing phenylphosphine oxide groups were exposed to low Earth orbit for approx.4 years. All of the aromatic polymers containing phenylphosphine oxide groups survived the exposure despite the high fluence of atomic oxygen that completely eroded other polymer films such as Kapton(TradeMark) and Mylar(Trademark) of comparable or greater thickness. The samples were characterized for changes in physical properties, thermal/optical properties surface chemistry, and surface topography. The data from the polymer samples on MISSE were compared to samples from the same batch of material stored under ambient conditions on Earth. In addition, comparisons were made between the MISSE samples and those subjected to shorter term space flight exposures. The results of these analyses will be presented.

Effects of excipients on the tensile strength, surface properties and free volume of Klucel® free films of pharmaceutical importance

NASA Astrophysics Data System (ADS)

Gottnek, Mihály; Süvegh, Károly; Pintye-Hódi, Klára; Regdon, Géza

2013-08-01

The physicochemical properties of polymers planned to be applied as mucoadhesive films were studied. Two types of Klucel® hydroxypropylcellulose (LF and MF) were used as film-forming polymers. Hydroxypropylcellulose was incorporated in 2 w/w% with glycerol and xylitol as excipients and lidocaine base as an active ingredient at 5, 10 or 15 w/w% of the mass of the film-forming polymer. The free volume changes of the films were investigated by positron annihilation lifetime spectroscopy, the mechanical properties of the samples were measured with a tensile strength tester and contact angles were determined to assess the surface properties of the films. It was found that the Klucel® MF films had better physicochemical properties than those of the LF films. Klucel® MF as a film-forming polymer with lidocaine base and both excipients at 5 w/w% exhibited physicochemical properties and good workability. The excipients proved to exert strong effects on the physicochemical properties of the tested systems and it is very important to study them intensively in preformulation studies in the pharmaceutical technology in order to utilise their benefits and to avoid any disadvantageous effects.

Antifouling Properties of Fluoropolymer Brushes toward Organic Polymers: The Influence of Composition, Thickness, Brush Architecture, and Annealing.

PubMed

Wang, Zhanhua; Zuilhof, Han

2016-07-05

Fluoropolymer brushes are widely used to prevent nonspecific adsorption of commercial polymeric or biological materials due to their strongly hydrophobic character. Herein, a series of fluoropolymer brushes with different compositions, thicknesses and molecular architectures was prepared via surface-initiated atom transfer radical polymerization (ATRP). Subsequently, the antifouling properties of these fluoropolymer brushes against organic polymers were studied in detail using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) measurements and polystyrene as a representative fouling polymer. Among all of the molecular architectures studied, homopolymerized methacrylate-based fluoropolymer brushes (PMAF17) show the best antifouling properties. Annealing the fluoropolymer brushes improves the antifouling property dramatically due to the reregulated surface composition. These fluoropolymer brushes can be combined with, e.g., micro- and nanostructuring and other advanced materials properties to yield even better long-term antifouling behavior under harsh environments.

Graphene and Polymer Composites for Supercapacitor Applications: a Review

NASA Astrophysics Data System (ADS)

Gao, Yang

2017-06-01

Supercapacitors, as one of the energy storage devices, exhibit ultrahigh capacitance, high power density, and long cycle. High specific surface area, mechanical and chemical stability, and low cost are often required for supercapacitor materials. Graphene, as a new emerging carbon material, has attracted a lot of attention in energy storage field due to its intrinsic properties. Polymers are often incorporated into graphene for a number of enhanced or new properties as supercapacitors. In this paper, different polymers which are used to form composite materials for supercapacitor applications are reviewed. The functions, strategies, and the enhanced properties of graphene and polymer composites are discussed. Finally, the recent development of graphene and polymers for flexible supercapacitors are also discussed.

Solution Exchange Lithography: A Versatile Tool for Sequential Surface Engineering

NASA Astrophysics Data System (ADS)

Pester, Christian; Mattson, Kaila; Bothman, David; Klinger, Daniel; Lee, Kenneth; Discekici, Emre; Narupai, Benjaporn; Hawker, Craig

The covalent attachment of polymers has emerged as a viable strategy for the preparation of multi-functional surfaces. Patterned, surface-grafted polymer brushes provide spatial control over wetting, mechanical, biological or electronic properties, and allow fabrication of `intelligent' substrates which selectively adapt to their environment. However, the route towards patterned polymer brush surfaces often remains challenging, creating a demand for more efficient and less complicated fabrication strategies. We describe the design and application of a novel experimental setup to combine light-mediated and flow chemistry for the fabrication of hierarchical surface-grafted polymer brushes. Using light-mediated, surface initiated controlled radical polymerization and post-functionalization via well-established, and highly efficient chemistries, polymer brush films of previously unimaginable complexity are now shown to be accessible. This methodology allows full flexibility to exchange both lithographic photomasks and chemical environments in-situ, readily affording multidimensional thin film architectures, all from uniformly functionalized substrates.

Organic Chemistry in Two Dimensions: Surface-Functionalized Polymers and Self-Assembled Monolayer Films

DTIC Science & Technology

1988-09-01

surfaces as components of materials . In particular, we hope to develop the ability to rationalize and predict the macroscooic properties of surfaces...of much of the current research in areas such as materials science, condensed matter and device physics, and polymer physical chemistry. Surface...6 Underlying our program in surface chemistry is a broad interest in the prop- erties of organic surfaces as components of materials . In particular

Surface modification of polymers for biocompatibility via exposure to extreme ultraviolet radiation.

PubMed

Inam Ul Ahad; Bartnik, Andrzej; Fiedorowicz, Henryk; Kostecki, Jerzy; Korczyc, Barbara; Ciach, Tomasz; Brabazon, Dermot

2014-09-01

Polymeric biomaterials are being widely used for the treatment of various traumata, diseases and defects in human beings due to ease in their synthesis. As biomaterials have direct interaction with the extracellular environment in the biological world, biocompatibility is a topic of great significance. The introduction or enhancement of biocompatibility in certain polymers is still a challenge to overcome. Polymer biocompatibility can be controlled by surface modification. Various physical and chemical methods (e.g., chemical and plasma treatment, ion implantation, and ultraviolet irradiation etc.) are in use or being developed for the modification of polymer surfaces. However an important limitation in their employment is the alteration of bulk material. Different surface and bulk properties of biomaterials are often desirable for biomedical applications. Because extreme ultraviolet (EUV) radiation penetration is quite limited even in low density mediums, it could be possible to use it for surface modification without influencing the bulk material. This article reviews the degree of biocompatibility of different polymeric biomaterials being currently employed in various biomedical applications, the surface properties required to be modified for biocompatibility control, plasma and laser ablation based surface modification techniques, and research studies indicating possible use of EUV for enhancing biocompatibility. © 2013 Wiley Periodicals, Inc.

Zwitterionic sulfobetaine polymer-immobilized surface by simple tyrosinase-mediated grafting for enhanced antifouling property.

PubMed

Kwon, Ho Joon; Lee, Yunki; Phuong, Le Thi; Seon, Gyeung Mi; Kim, Eunsuk; Park, Jong Chul; Yoon, Hyunjin; Park, Ki Dong

2017-10-01

Introducing antifouling property to biomaterial surfaces has been considered an effective method for preventing the failure of implanted devices. In order to achieve this, the immobilization of zwitterions on biomaterial surfaces has been proven to be an excellent way of improving anti-adhesive potency. In this study, poly(sulfobetaine-co-tyramine), a tyramine-conjugated sulfobetaine polymer, was synthesized and simply grafted onto the surface of polyurethane via a tyrosinase-mediated reaction. Surface characterization by water contact angle measurements, X-ray photoelectron spectroscopy and atomic force microscopy demonstrated that the zwitterionic polymer was successfully introduced onto the surface of polyurethane and remained stable for 7days. In vitro studies revealed that poly(sulfobetaine-co-tyramine)-coated surfaces dramatically reduced the adhesion of fibrinogen, platelets, fibroblasts, and S. aureus by over 90% in comparison with bare surfaces. These results proved that polyurethane surfaces grafted with poly(sulfobetaine-co-tyramine) via a tyrosinase-catalyzed reaction could be promising candidates for an implantable medical device with excellent bioinert abilities. Antifouling surface modification is one of the key strategy to prevent the thrombus formation or infection which occurs on the surface of biomaterial after transplantation. Although there are many methods to modify the surface have been reported, necessity of simple modification technique still exists to apply for practical applications. The purpose of this study is to modify the biomaterial's surface by simply immobilizing antifouling zwitterion polymer via enzyme tyrosinase-mediated reaction which could modify versatile substrates in mild aqueous condition within fast time period. After modification, pSBTA grafted surface becomes resistant to various biological factors including proteins, cells, and bacterias. This approach appears to be a promising method to impart antifouling property on biomaterial surfaces. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

The Art and Science of Polymer Brushes: Recent Developments in Patterning and Characterization Approaches.

PubMed

Panzarasa, Guido

2017-06-28

Polymer brushes are dense arrays of macromolecular chains tethered by one end at a surface. They are at the cutting edge of polymer nanotechnology since the dawn of controlled surface-initiated polymerization techniques unlocked new prospects for the synthesis of polymer brushes with tailorable properties. More recently, thanks to the growing interest in the use of brushes for the generation of functional surfaces, the need for advanced patterning and characterization approaches rapidly increased. Meeting these needs requires the contribution of experts from different disciplines: polymer chemistry, surface science, electrochemistry and particle physics. The focus of this review is to highlight recent developments in the field of polymer brushes, specifically the application of photocatalytic lithography as a versatile patterning strategy, the study of grafted-from polymer brushes by electrochemical methods and, most importantly, the introduction of positron annihilation spectroscopy as a powerful technique for the investigation of the structure of polymer brushes and of their composites with nanoparticles.

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

Martinez, Andre P.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.

The molecular weight and polydispersity of the chains in a polymer brush are critical parameters determining the brush properties. However, the characterization of polymer brushes is hindered by the vanishingly small mass of polymer present in brush layers. In this study, in order to obtain sufficient quantities of polymer for analysis, polymer brushes were grown from high surface area fibrous nylon membranes by ATRP. We synthesized the brushes with varying surface initiator densities, polymerization times, and amounts of sacrificial initiator, then cleaved from the substrate, and analyzed by GPC and NMR. Characterization showed that the surface-grown polymer chains were moremore » polydisperse and had lower average molecular weight compared to solution-grown polymers synthesized concurrently. Furthermore, the molecular weight distribution of the polymer brushes was observed to be bimodal, with a low molecular weight population of chains representing a significant mass fraction of the polymer chains at high surface initiator densities. Moreover, the origin of this low MW polymer fraction is proposed to be the termination of growing chains by recombination during the early stages of polymerization, a mechanism confirmed by molecular dynamics simulations of brush polymerization.« less

Plasma-modified graphene nanoplatelets and multiwalled carbon nanotubes as fillers for advanced rubber composites

NASA Astrophysics Data System (ADS)

Sicinski, M.; Gozdek, T.; Bielinski, D. M.; Szymanowski, H.; Kleczewska, J.; Piatkowska, A.

2015-07-01

In modern rubber industry, there still is a room for new fillers, which can improve the mechanical properties of the composites, or introduce a new function to the material. Modern fillers like carbon nanotubes or graphene nanoplatelets (GnP), are increasingly applied in advanced polymer composites technology. However, it might be hard to obtain a well dispersed system for such systems. The polymer matrix often exhibits higher surface free energy (SFE) level with the filler, which can cause problems with polymer-filler interphase adhesion. Filler particles are not wet properly by the polymer, and thus are easier to agglomerate. As a consequence, improvement in the mechanical properties is lower than expected. In this work, multi-walled carbon nanotubes (MWCNT) and GnP surface were modified with low-temperature plasma. Attempts were made to graft some functionalizing species on plasma-activated filler surface. The analysis of virgin and modified fillers’ SFE was carried out. MWCNT and GnP rubber composites were produced, and ultimately, their morphology and mechanical properties were studied.

Bioinspired Nanocellulose Based Hybrid Materials With Novel Interfacial Properties

NASA Astrophysics Data System (ADS)

Keten, Sinan

This talk will overview a simulation-based approach to enhancing the mechanical properties of nanocomposites by utilizing cellulose - the most abundant and renewable structural biopolymer found on our planet. Cellulose nanocrystals (CNCs) exhibit outstanding mechanical properties exceeding that of Kevlar, serving as reinforcing domains in nature's toughest hierarchical nanocomposites such as wood. Yet, weak interfaces at the surfaces of CNCs have so far made it impossible to scale these inherent properties to macroscopic systems. In this work, I will discuss how surface functionalization of CNCs influences their properties in their self-assembled films and nanocomposites with engineered polymer matrices . Specifically, the role of ion exchange based surface modifications and polymer conjugation will be discussed, where atomistic and coarse-grained simulations will reveal new insights into how superior mechanical properties can potentially be attained by hybrid constructs.

Amino acid-based zwitterionic polymers: antifouling properties and low cytotoxicity.

PubMed

Li, Wenchen; Liu, Qingsheng; Liu, Lingyun

2014-01-01

A group of five amino acid containing zwitterionic vinyl monomers, based on serine, lysine, ornithine, glutamic acid, and aspartic acid, respectively, were proposed and developed for potential antifouling applications. Their polymer brushes were grafted on gold chips by surface-initiated photoiniferter-mediated polymerization. We then compared their performance in resisting protein adsorption from full human serum and plasma. All five polymers can reduce protein adsorption by more than 90% compared to the unmodified gold. The ornithine-based and aspartic acid-based poly(methacrylamide) can most strongly resist protein adsorption from serum and plasma, compared to the other three. The ability of surfaces to suppress bacterial adhesion is another criterion in evaluating antifouling properties of materials. Our results show that the five polymer-grafted surfaces can significantly suppress Escherichia coli K12 adhesion to 99% compared to the bare gold surface. The zwitterionic structure of amino acids, with homogenously distributed and balanced positive and negative charges, is responsible for the outstanding antifouling properties. Considering multiple potential applications (e.g. medical devices and drug delivery) of the antifouling materials, we further systematically evaluated the cytotoxicity of both monomers and polymer nanogels for all five materials at various concentrations. Very low cytotoxicity was observed for all tested amino acid-based monomers and nanogels, which is comparable or even lower than the traditional and some newly developed antifouling materials, which might be related to the biomimetic nature of amino acids.

Ultraviolet and thermally stable polymer compositions

NASA Technical Reports Server (NTRS)

Reinisch, R. F.; Gloria, H. R.; Goldsberry, R. E.; Adamson, M. J. (Inventor)

1976-01-01

A new class of polymers is provided, namely, poly (diarylsiloxy) arylazines. These novel polymers have a basic chemical composition which has the property of stabilizing the optical and physical properties of the polymer against the degradative effect of ultraviolet light and high temperatures. This stabilization occurs at wavelengths including those shorter than found on the surface of the earth and in the absence or presence of oxygen, making the polymers useful for high performance coating applications in extraterrestrial space as well as similar applications in terrestrial service. The invention also provides novel aromatic azines which are useful in the preparation of polymers such as those described.

Ultraviolet and thermally stable polymer compositions

NASA Technical Reports Server (NTRS)

Reinisch, R. F.; Gloria, H. R.; Goldsberry, R. E.; Adamson, M. J. (Inventor)

1974-01-01

A class of polymers is provided, namely, poly(diarylsiloxy) arylazines. These polymers have a basic chemical composition which has the property of stabilizing the optical and physical properties of the polymer against the degradative effect of ultraviolet light and high temperatures. This stabilization occurs at wavelengths including those shorter than found on the surface of the earth and in the absence or presence of oxygen, making the polymers of the present invention useful for high performance coating applications in extraterrestrial space as well as similar applications in terrestrial service. The invention also provides aromatic azines which are useful in the preparation of polymers such as those of the present invention.

Understanding the interfacial chain dynamics of fiber-reinforced polymer composite

NASA Astrophysics Data System (ADS)

Goswami, Monojoy; Carrillo, Jan-Michael; Naskar, Amit; Sumpter, Bobby

The polymer-fiber interface plays a major role in determining the structural and dynamical properties of fiber reinforced composite materials. We utilized LAMMPS MD package to understand the interfacial properties at the nanoscale. Coarse-grained flexible polymer chains are introduced to compare the various structures and dynamics of the polymer chains. Our preliminary simulation study shows that the rigidity of the polymer chain affects the interfacial morphology and dynamics of the chain on a flat surface. In this work, we identified the `immobile inter-phase' morphology and relate it to rheological properties. We calculated the viscoelastic properties, e.g., shear modulus and storage modulus, which are compared with experiments. MD simulations are used to show the variation of viscoelastic properties with polymer volume fraction. The nanoscale segmental and chain relaxation are calculated from the MD simulations and compared to the experimental data. These observations will be able to identify the fundamental physics behind the effect of the polymer-fiber interactions and orientation of the fiber to the overall rheological properties of the fiber reinforced polymer matrix. Funding for the project was provided by ORNLs Laboratory Directed Research and Development (LDRD) program.

Polymer adsorption on silica and wettability of graphene oxide surfaces, experiments and simulations

NASA Astrophysics Data System (ADS)

Mortazavian, Hamid

Among the various classifications of polymer composites, studying polymers adsorbed to a surface such as silica is important due to their numerous applications. Adsorbed polymers usually show different properties than their bulk counterparts due to their interactions with the surface. In this study, we observed tightly- and loosely-bound polymer and mobile components in poly(vinyl acetate) (PVAc) on silica both with temperature-modulated differential scanning calorimetry (TMDSC) experiments and computer simulations. The more-mobile component which correlated to the region of low density at the air interface is reported for the first time using TMDSC thermograms. Pore size distribution and pore volume development of adsorbed PMMA samples showed different behavior below and above the tightly-bound amount of the polymer. The amount of tightly-bound polymer was obtained by a linear regression analysis of the ratio of the area under the two glass transitions. The values obtained vary from 0.52 to 0.86 mg PVAc/m2 silica depending upon the molecular mass for the amounts of PVAc and the specific surface area of fumed silica. Direct comparisons of the thermal properties and intermolecular interactions were performed between PVAc and poly(methyl methacrylate) (PMMA) with similar molecular masses and adsorbed amounts on silica. A larger amount of tightly-bound polymer and a greater change in glass transition were observed for adsorbed PMMA compared to adsorbed PVAc. These observations suggested that the interactions between PMMA and silica were stronger than those between PVAc and silica. Molecular modeling of these surface polymers showed that PMMA associates more strongly with silica than does PVAc through additional hydrogen-bonding interactions. Graphene oxide (GO) material surface characteristics make it easy to functionalize, making it a water repellant surface. To test the effect of chemical makeup and size of attached groups on the surface wettability of GO, we performed experimental water contact angle measurements and molecular modeling investigations on functionalized GO surfaces. Experimental and molecular simulation water contact angle measurements showed quantitative agreement for functionalizing groups with the same chain length at a variety of surface coverages.

Behavior of grafted polymers on nanofillers and their influence on polymer nanocomposite properties

NASA Astrophysics Data System (ADS)

Dukes, Douglas Michael

Polymer nanocomposites continue to receive wide-spread acclaim for their potential to improve composite materials beyond conventional macroscale fillers. The improvement lies both in the altered properties of the particle itself and in the interaction region surrounding the filler. As the surface area of the filler increases, a greater volume fraction of this interphase region is present in the composite. However, simply minimizing the particle size to maximize surface area introduces additional problems; the larger specific surface area promotes aggregation to reduce the surface energy. Since the composite's properties are largely tied to the morphology, aggregation prevents control over the dispersion state of the filler, and thus the properties. Therefore, disaggregation and morphology control are vital to achieving designable nanocomposites. To accomplish both tasks, this thesis focuses on the behavior of grafted polymer coatings on nanoparticles and their in uence on the macroscopic properties. Grafted chains play an integral role in both morphology control and reinforcement. To investigate the behavior of polymer brushes on nanoparticles, polystyrene was grafted on 15 nm silica particles at varying graft densities and molecular weights. Dynamic light scattering studies in dilute solution were performed to obtain the brush height as a function of both graft density and molecular weight. Three distinct regimes of behavior exist, the "mushroom", the semi-dilute polymer brush (SDPB), and the concentrated polymer brush (CPB) regimes. In the CPB regime, which is an extraordinary configuration of highly-stretched chains on densely grafted surfaces, the brush height h was found to scale as h ∝ N4/5, where N is the degree of polymerization. This result is contrary to the observed scaling of the CPB in flat interface systems, where h ∝ N1. To explore the behavior of grafted chains in the melt, molecular dynamics simulations were performed on grafted nanoparticles grafted with varying amounts of polymer chains at different curvatures. Particles as small as 15 monomers in size were found to already be in the large particle limit, a result that has many implications regarding the dispersibility of grafted fillers in composites. At low graft densities, melt chains were found to form entanglements with the brush all the way to the particle surface, implying the particle is not effectively screened by the grafted chains. The mechanical properties of these grafted silica composites were studied as a function of matrix polymer fraction. As more matrix polymer is introduced, the dominant contribution to the behavior shifts from the grafted chains to the matrix chains. This elucidates the role of grafted chains on the mechanical properties of grafted nanoparticle composites. As the graft density is increased, the wettability of grafted chains was shown to decrease, causing fewer entanglements between grafted chains and matrix chains, resulting in poorer reinforcement. Interesting behavior was observed at low graft densities; a pronounced shape memory effect occurred at high particle concentrations. It is proposed that the grafted chains entangle with adjacent grafted chains, forming a three-dimensional network of entangled brushes attached to silica cores. This structure effectively forms "cross-links" as in elastomeric systems, giving an entropic restorative force to stretched chains. Thus, above Tg, when chains have a higher degree of mobility, the composites can be stretched to over 800%. When cooled to below Tg, they retain the deformed geometry. Upon reheating above Tg, the composite is restored to its original dimensions. This work has identified means of improving theoretical models to better guide future experiments and lead to predictability in polymer composite design. Grafted chains have the demonstrated ability to control the morphology and reinforcement in polymer composites. The behavior of grafted chains were shown to demonstrate drastically different properties from their bulk polymer counterparts.

Development of Functional Surfaces on High-Density Polyethylene (HDPE) via Gas-Assisted Etching (GAE) Using Focused Ion Beams.

PubMed

Sezen, Meltem; Bakan, Feray

2015-12-01

Irradiation damage, caused by the use of beams in electron and ion microscopes, leads to undesired physical/chemical material property changes or uncontrollable modification of structures. Particularly, soft matter such as polymers or biological materials is highly susceptible and very much prone to react on electron/ion beam irradiation. Nevertheless, it is possible to turn degradation-dependent physical/chemical changes from negative to positive use when materials are intentionally exposed to beams. Especially, controllable surface modification allows tuning of surface properties for targeted purposes and thus provides the use of ultimate materials and their systems at the micro/nanoscale for creating functional surfaces. In this work, XeF2 and I2 gases were used in the focused ion beam scanning electron microscope instrument in combination with gallium ion etching of high-density polyethylene surfaces with different beam currents and accordingly different gas exposure times resulting at the same ion dose to optimize and develop new polymer surface properties and to create functional polymer surfaces. Alterations in the surface morphologies and surface chemistry due to gas-assisted etching-based nanostructuring with various processing parameters were tracked using high-resolution SEM imaging, complementary energy-dispersive spectroscopic analyses, and atomic force microscopic investigations.

Polymer Brushes as Functional, Patterned Surfaces for Nanobiotechnology.

PubMed

Welch, M Elizabeth; Xu, Youyong; Chen, Hongjun; Smith, Norah; Tague, Michele E; Abruña, Héctor D; Baird, Barbara; Ober, Christopher K

2013-01-01

Polymer brushes have many desirable characteristics such as the ability to tether molecules to a substrate or change the properties of a surface. Patterning of polymer films has been an area of great interest due to the broad range of applications including bio-related and medicinal research. Consequently, we have investigated patterning techniques for polymer brushes which allow for two different functionalities on the same surface. This method has been applied to a biosensor device which requires both polymer brushes and a photosensitizer to be polymerized on a patterned gold substrate. Additionally, the nature of patterned polymer brushes as removable thin films was explored. An etching process has enabled us to lift off very thin membranes for further characterization with the potential of using them as Janus membranes for biological applications.

Aggregation, adsorption, and surface properties of multiply end-functionalized polystyrenes.

PubMed

Ansari, Imtiyaz A; Clarke, Nigel; Hutchings, Lian R; Pillay-Narrainen, Amilcar; Terry, Ann E; Thompson, Richard L; Webster, John R P

2007-04-10

The properties of polystyrene blends containing deuteriopolystyrene, multiply end-functionalized with C8F17 fluorocarbon groups, are strikingly analogous to those of surfactants in solution. These materials, denoted FxdPSy, where x is the number of fluorocarbon groups and y is the molecular weight of the dPS chain in kg/mol, were blended with unfunctionalized polystyrene, hPS. Nuclear reaction analysis experiments show that FxdPSy polymers adsorb spontaneously to solution and blend surfaces, resulting in a reduction in surface energy inferred from contact angle analysis. Aggregation of functionalized polymers in the bulk was found to be sensitive to FxdPSy structure and closely related to surface properties. At low concentrations, the functionalized polymers are freely dispersed in the hPS matrix, and in this range, the surface excess concentration grows sharply with increasing bulk concentration. At higher concentrations, surface excess concentrations and contact angles reach a plateau, small-angle neutron scattering data indicate small micellar aggregates of six to seven F2dPS10 polymer chains and much larger aggregates of F4dPS10. Whereas F2dPS10 aggregates are miscible with the hPS matrix, F4dPS10 forms a separate phase of multilamellar vesicles. Using neutron reflectometry (NR), we found that the extent of the adsorbed layer was approximately half the lamellar spacing of the multilamellar vesicles. NR data were fitted using an error function profile to describe the concentration profile of the adsorbed layer, and reasonable agreement was found with concentration profiles predicted by the SCFT model. The thermodynamic sticking energy of the fluorocarbon-functionalized polymer chains to the blend surface increases from 5.3kBT for x = 2 to 6.6kBT for x = 4 but appears to be somewhat dependent upon the blend concentration.

Surface engineering of ferroelectric polymer for the enhanced electrical performance of organic transistor memory

NASA Astrophysics Data System (ADS)

Kim, Do-Kyung; Lee, Gyu-Jeong; Lee, Jae-Hyun; Kim, Min-Hoi; Bae, Jin-Hyuk

2018-05-01

We suggest a viable surface control method to improve the electrical properties of organic nonvolatile memory transistors. For viable surface control, the surface of the ferroelectric insulator in the memory field-effect transistors was modified using a smooth-contact-curing process. For the modification of the ferroelectric polymer, during the curing of the ferroelectric insulators, the smooth surface of a soft elastomer contacts intimately with the ferroelectric surface. This smooth-contact-curing process reduced the surface roughness of the ferroelectric insulator without degrading its ferroelectric properties. The reduced roughness of the ferroelectric insulator increases the mobility of the organic field-effect transistor by approximately eight times, which results in a high memory on–off ratio and a low-voltage reading operation.

A short review of radiation-induced raft-mediated graft copolymerization: A powerful combination for modifying the surface properties of polymers in a controlled manner

NASA Astrophysics Data System (ADS)

Barsbay, Murat; Güven, Olgun

2009-12-01

Surface grafting of polymeric materials is attracting increasing attention as it enables the preparation of new materials from known and commercially available polymers having desirable bulk properties such as thermal stability, elasticity, permeability, etc., in conjunction with advantageous newly tailored surface properties such as biocompatibility, biomimicry, adhesion, etc. Ionizing radiation, particularly γ radiation is one of the most powerful tools for preparing graft copolymers as it generates radicals on most substrates. With the advent of living free-radical polymerization techniques, application of γ radiation has been extended to a new era of grafting; grafting in a controlled manner to achieve surfaces with tailored and well-defined properties. This report presents the current use of γ radiation in living free-radical polymerization and highlights the use of both techniques together as a combination to present an advance in the ability to prepare surfaces with desired, tunable and well-defined properties.

Gold Nanoparticles with Externally Controlled, Reversible Shifts of Local Surface Plasmon Resonance Bands

PubMed Central

Yavuz, Mustafa S.; Jensen, Gary C.; Penaloza, David P.; Seery, Thomas A. P.; Pendergraph, Samuel A.; Rusling, James F.; Sotzing, Gregory A.

2010-01-01

We have achieved reversible tunability of local surface plasmon resonance in conjugated polymer functionalized gold nanoparticles. This property was facilitated by the preparation of 3,4-ethylenedioxythiophene (EDOT) containing polynorbornene brushes on gold nanoparticles via surface-initiated ring-opening metathesis polymerization. Reversible tuning of the surface plasmon band was achieved by electrochemically switching the EDOT polymer between its reduced and oxidized states. PMID:19839619

Effect of polymer properties and adherend surfaces on adhesion

NASA Technical Reports Server (NTRS)

Dwight, D. W.; Wightman, J. P.

1976-01-01

High temperature polymer surface characteristics associated with joint strength were evaluated. Selected samples represented composite adherends, aluminum filler and fiber glass carrier cloth. Detailed analysis of fractured joint surfaces revealed unique characteristics typical of the specific adhesive formulations and test conditions. A fracture mechanism model was developed for correlating macroscopic shear strength and microstructure of fracture surfaces. Applications were made to unpublished data on polyimides and fluoropolymers.

Physical and chemical properties of some new perfluoropolyalkylether lubricants prepared by direct fluorination

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.; Bierschenk, T. R.; Juhlke, T. J.; Kawa, H.; Lagow, R. J.

1993-01-01

A series of perfluoropolyalkylether (PFPAE) fluids was synthesized by direct fluorination. Viscosity-temperature properties, oxidation stabilities, oxidation-corrosion properties, bulk modulus, lubricity, surface tension and density were measured. It was shown that as the carbon to oxygen ratio in the polymer repeating unit decreases, the viscometric properties improve, the fluids may become poorer boundary lubricants, the bulk modulus increases, the surface tension increases and the fluid density increases. The presence of difluoromethylene oxide units in the polymer does not significantly lower the oxidation and oxidation-corrosion stabilities as long as the difluoromethylene oxide units are separated by other units.

Ultraviolet-induced surface grafting of octafluoropentyl methacrylate on polyether ether ketone for inducing antibiofilm properties.

PubMed

Amdjadi, Parisa; Nojehdehian, Hanieh; Najafi, Farhood; Ghasemi, Amir; Seifi, Massoud; Dashtimoghadam, Erfan; Fahimipour, Farahnaz; Tayebi, Lobat

2017-07-01

Since octafluoropentyl methacrylate is an antifouling polymer, surface modification of polyether ether ketone with octafluoropentyl methacrylate is a practical approach to obtaining anti-biofilm biocompatible devices. In the current study, the surface treatment of polyether ether ketone by the use of ultraviolet irradiation, so as to graft (octafluoropentyl methacrylate) polymer chains, was initially implemented and then investigated. The Fourier-transform infrared and nuclear magnetic resonance spectra corroborated the appearance of new signals associated with the fluoroacrylate group. Thermogravimetric curves indicated enhanced asymmetry in the polymer structure due to the introduction of the said new groups. Measuring the peak area in differential scanning calorimetry experiments also showed additional bond formation. Static water contact angle measurements indicated a change in wettability to the more hydrophobic surface. The polyether ether ketone-octafluoropentyl methacrylate surface greatly reduced the protein adsorption. This efficient method can modulate and tune the surface properties of polyether ether ketone according to specific applications.

Distribution of Chains in Polymer Brushes Produced by a “Grafting From” Mechanism

DOE PAGES

Martinez, Andre P.; Carrillo, Jan-Michael Y.; Dobrynin, Andrey V.; ...

2016-01-11

The molecular weight and polydispersity of the chains in a polymer brush are critical parameters determining the brush properties. However, the characterization of polymer brushes is hindered by the vanishingly small mass of polymer present in brush layers. In this study, in order to obtain sufficient quantities of polymer for analysis, polymer brushes were grown from high surface area fibrous nylon membranes by ATRP. We synthesized the brushes with varying surface initiator densities, polymerization times, and amounts of sacrificial initiator, then cleaved from the substrate, and analyzed by GPC and NMR. Characterization showed that the surface-grown polymer chains were moremore » polydisperse and had lower average molecular weight compared to solution-grown polymers synthesized concurrently. Furthermore, the molecular weight distribution of the polymer brushes was observed to be bimodal, with a low molecular weight population of chains representing a significant mass fraction of the polymer chains at high surface initiator densities. Moreover, the origin of this low MW polymer fraction is proposed to be the termination of growing chains by recombination during the early stages of polymerization, a mechanism confirmed by molecular dynamics simulations of brush polymerization.« less

Development of Biomimetic and Functionally Responsive Surfaces

NASA Astrophysics Data System (ADS)

Anastasiadis, Spiros H.

2010-03-01

Controlling the surface morphology of solids and manufacturing of functional surfaces with special responsive properties has been the subject of intense research. We report a methodology for creating multifunctionally responsive surfaces by irradiating silicon wafers with femtosecond laser pulses and subsequently coating them with different types of functional conformal coatings. Such surfaces exhibit controlled dual-scale roughness at the micro- and the nano-scale, which mimics the hierarchical morphology of water repellent natural surfaces. When a simple alkylsilane coating is utilized, highly water repellent surfaces are produced that quantitatively compare to those of the Lotus leaf. When a polymer brush is ``grafted from" these surfaces based on a pH-sensitive polymer, the surfaces can alter their behavior from super-hydrophilic (after immersion in a low pH buffer) to super-hydrophobic and water-repellent (following immersion to a high pH buffer). We quantify the water repellency of such responsive systems by drop elasticity measurements whereas we demonstrate that the water repellent state of such surface requires appropriate hydrophobicity of the functionalizing polymer. When a photo-responsive azobenzene-type polymer is deposited, a dynamic optical control of the wetting properties is obtained and the surface can be switched from super-hydrophilic (following UV irradiation) to hydrophobic (following green irradiation). In all the above cases we show that the principal effect of roughness is to cause amplification of the response to the different external stimuli.

Artificial neural network based particle size prediction of polymeric nanoparticles.

PubMed

Youshia, John; Ali, Mohamed Ehab; Lamprecht, Alf

2017-10-01

Particle size of nanoparticles and the respective polydispersity are key factors influencing their biopharmaceutical behavior in a large variety of therapeutic applications. Predicting these attributes would skip many preliminary studies usually required to optimize formulations. The aim was to build a mathematical model capable of predicting the particle size of polymeric nanoparticles produced by a pharmaceutical polymer of choice. Polymer properties controlling the particle size were identified as molecular weight, hydrophobicity and surface activity, and were quantified by measuring polymer viscosity, contact angle and interfacial tension, respectively. A model was built using artificial neural network including these properties as input with particle size and polydispersity index as output. The established model successfully predicted particle size of nanoparticles covering a range of 70-400nm prepared from other polymers. The percentage bias for particle prediction was 2%, 4% and 6%, for the training, validation and testing data, respectively. Polymer surface activity was found to have the highest impact on the particle size followed by viscosity and finally hydrophobicity. Results of this study successfully highlighted polymer properties affecting particle size and confirmed the usefulness of artificial neural networks in predicting the particle size and polydispersity of polymeric nanoparticles. Copyright © 2017 Elsevier B.V. All rights reserved.

Fabrication of flexible gold nanorods polymer metafilm via phase transfer method as SERS substrate for detecting food contaminants.

PubMed

Yang, Nan; You, Ting-Ting; Gao, Yu-Kun; Zhang, Chen-Meng; Yin, Penggang

2018-06-08

Surface enhanced Raman scattering (SERS) has been widely used in detection of food safety due to the nondestructive examination property. Here, we reported a flexible SERS film based on polymer immobilized gold nanorods polymer metafilm. Polystyrene-polyisoprene-polystyrene (SIS), a transparent and flexible along with excellent elasticity polymer was chosen as main support of gold nanorods. A simple phase transfer progress was adopted to mix the gold nanorods with polymer which can further used in most water-insoluble polymers. The SERS film performed satisfactorily while tested in a series of standard Raman probes like crystal violet (CV) and malachite green (MG). Moreover, the excellent reproducibility and elastic properties make the film promising substrates in practical detection. Hence, the MG detection on fish surface and trace thiram detection on orange pericarp were inspected with the detection result of 1 × 10-10 M and 1 × 10-6 M which below the demand of National standard of China, exactly matching the realistic application requirements.

Understanding the adhesion and optical properties of eutectic metal alloys for solution-processed electronics

NASA Astrophysics Data System (ADS)

Kumar, Prashant; Aggarwal, Shantanu; Narayana, Chandrabhas; Narayan, K. S.

2018-02-01

The role of indium in controlling the adhesion and the optical properties of fusible, low- melting alloys is highlighted in this work. The optical activity of indium-alloy/polymer interface is probed using surface-enhanced Raman spectroscopy, which shows a large increase in polymer Raman modes intensity. Signatures of plasmon and chemically enhanced Raman are visible for more than one polymer. Improvement in adhesion is also reflected in their ability to coat conformally onto the polymer surface resulting in a suitable interface for electrical transport. The electrical characteristics of alloy electrodes, which are printed in ambient conditions, are superior when compared to the thermally evaporated aluminum cathodes. Raman and responsivity measurements indicate that indium (In) forms metal/organic hybrid charge-transfer states at the alloy/polymer interface and assumes a decisive role in controlling the mechanical, optical, and electrical properties of these electrodes. Our studies suggest that the indium present in small quantities (˜5 wt. %) can significantly improve the overall performance of the low-temperature printable eutectic alloy electrodes.

[Use of a novel polymer, the in-situ gelling mucoadhesive thiolated poly(aspartic acid) in ophthalmic drug delivery].

PubMed

Horvát, Gabriella; Budai-Szűcs, Mária; Berkó, Szilvia; Szabóné-Révész, Piroska; Gyarmati, Benjámin; Szilágyi, Barnabas Áron; Szilágyi, András; Csányi Erzsébet

2015-01-01

The bioavailability of drugs used on mucosal surfaces can be increased by the use of mucoadhesive polymers. A new type of mucoadhesive polymers is the group of thiolated polymers with thiol group containing side chains. These polymers are able to form covalent bonds (disulphide linkages) with the mucin glycoproteins. For the formulation of an ocular drug delivery system (DDS) thiolated poly(aspartic acid) polymer (ThioPASP) was used. Our aim was to determine their biocompatibility, mucoadhesion and drug release property. According to the results it can be established that the thiolated poly(aspartic acid) polymers can be a potential vehicle of an ocular drug delivery system due to their biocompatibility, good mucoadhesive property and drug release profile. Thanks to their properties controlled drug delivery can be achieved and bioavailability of the ophthalmic formulation can be increased, while the usage frequency can be decreased.

Polymer Layered Silicate Nanocomposites: A Review

PubMed Central

Mittal, Vikas

2009-01-01

This review aims to present recent advances in the synthesis and structure characterization as well as the properties of polymer layered silicate nanocomposites. The advent of polymer layered silicate nanocomposites has revolutionized research into polymer composite materials. Nanocomposites are organic-inorganic hybrid materials in which at least one dimension of the filler is less than 100 nm. A number of synthesis routes have been developed in the recent years to prepare these materials, which include intercalation of polymers or pre-polymers from solution, in-situ polymerization, melt intercalation etc. The nanocomposites where the filler platelets can be dispersed in the polymer at the nanometer scale owing to the specific filler surface modifications, exhibit significant improvement in the composite properties, which include enhanced mechanical strength, gas barrier, thermal stability, flame retardancy etc. Only a small amount of filler is generally required for the enhancement in the properties, which helps the composite materials retain transparency and low density.

Critical Role of Surface Energy in Guiding Crystallization of Solution-Coated Conjugated Polymer Thin Films

DOE PAGES

Zhang, Fengjiao; Mohammadi, Erfan; Luo, Xuyi; ...

2017-10-02

It is well-known that substrate surface properties have a profound impact on morphology of thin films solution coated atop and the resulting solid-state properties. However, design rules for guiding the substrate selection have not yet been established. Such design rules are particularly important for solution coated semiconducting polymers, as the substratedirected thin film morphology can impact charge transport properties by orders of magnitude. We hypothesize that substrate surface energies dictate the thin film morphology by modulating the free energy barrier to heterogeneous nucleation. To test this hypothesis, we systematically vary the substrate surface energy via surface functionalization techniques. We performmore » in-depth morphology and device characterizations to establish the relationship between substrate surface energy, thin film morphology and charge transport properties, employing a donor-accepter (D-A) conjugated polymer. Here, we find that decreasing the substrate surface energy progressively increases thin film crystallinity, degree of molecular ordering and extent of domain alignment. Notably, the enhanced morphology on the lowest surface energy substrate lead to a 10-fold increase in the charge carrier mobility. We further develop a free energy model relating the substrate surface energy to the penalty of heterogeneous nucleation from solution in the thin film geometry. The model correctly predicts the experimental trend, thereby validating our hypothesis. This work is a significant step towards establishing design rules and understanding the critical role of substrates in determining morphology of solution coated thin films.« less

Critical Role of Surface Energy in Guiding Crystallization of Solution-Coated Conjugated Polymer Thin Films

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

Zhang, Fengjiao; Mohammadi, Erfan; Luo, Xuyi

It is well-known that substrate surface properties have a profound impact on morphology of thin films solution coated atop and the resulting solid-state properties. However, design rules for guiding the substrate selection have not yet been established. Such design rules are particularly important for solution coated semiconducting polymers, as the substratedirected thin film morphology can impact charge transport properties by orders of magnitude. We hypothesize that substrate surface energies dictate the thin film morphology by modulating the free energy barrier to heterogeneous nucleation. To test this hypothesis, we systematically vary the substrate surface energy via surface functionalization techniques. We performmore » in-depth morphology and device characterizations to establish the relationship between substrate surface energy, thin film morphology and charge transport properties, employing a donor-accepter (D-A) conjugated polymer. Here, we find that decreasing the substrate surface energy progressively increases thin film crystallinity, degree of molecular ordering and extent of domain alignment. Notably, the enhanced morphology on the lowest surface energy substrate lead to a 10-fold increase in the charge carrier mobility. We further develop a free energy model relating the substrate surface energy to the penalty of heterogeneous nucleation from solution in the thin film geometry. The model correctly predicts the experimental trend, thereby validating our hypothesis. This work is a significant step towards establishing design rules and understanding the critical role of substrates in determining morphology of solution coated thin films.« less

Polymer subtrates for dry-coupled ultrasonic transducers

NASA Astrophysics Data System (ADS)

Komsky, Igor N.

2003-07-01

Dry-coupled inspection techniques are very important for applications on components with non-uniform surfaces and for inspections of advanced materials or coatings that are porous or otherwise sensitive to the application of water, gel, or some other ultrasonic couplants. To overcome the problems associated with the liquid coupling medium, a number of polymer films have been developed to transmit the ultrasound through a dry interface. These materials are very flexible so even low pressure loading is sufficient to adapt the films to the irregular inspection surfaces. Several polymer films have been evaluated to develop dry-coupled substrates for transducer modules. The modules will be utilized to detect and characterize fatigue cracks and corrosion spots in the aircraft structures. Ultrasonic properties of the polymer films were measured and compared with the properties of plastic or rubber-like materials commonly used for ultrasonic applications. Experiments have been carried out to analyze propagation of longitudinal and shear waves in the films. Two different types of the ultrasonic modules with the flexible polymer substrates are being developed. The influence of the surface condition on the module performance was evaluated for both types of the modules.

Bioorthogonal layer-by-layer encapsulation of pancreatic islets via hyperbranched polymers

PubMed Central

Gattás-Asfura, Kerim M.; Stabler, Cherie L.

2013-01-01

The encapsulation of viable tissues via layer-by-layer polymer assembly provides a versatile platform for cell surface engineering, with nanoscale control over capsule properties. Herein, we report the development of a hyperbranched polymer-based, ultrathin capsule architecture expressing bioorthogonal functionality and tailored physiochemical properties. Random carbodiimide-based condensation of 3,5-dicarboxyphenyl glycineamide on alginate yielded a highly branched polysaccharide with multiple, spatially restricted, and readily functionalizable terminal carboxylate moieties. Poly(ethylene glycol) (PEG) was utilized to link azido end groups to the structured alginate. Together with phosphine functionalized poly(amido amine) (PAMAM) dendrimer, nanoscale layer-by-layer coatings, covalently stabilized via Staudinger ligation, were assembled onto solid surfaces and pancreatic islets. The effects of electrostatic and/or bioorthogonal covalent interlayer interactions on the resulting coating efficiency and stability, as well as pancreatic islet viability and function, were studied. These hyperbranched polymers provide a flexible platform for the formation of covalently stabilized ultrathin coatings on viable cells and tissues. In addition, the hyperbranched nature of the polymers presents a highly functionalized surface capable of bioorthogonal conjugation of additional bioactive or labeling motifs. PMID:24063764

Physical properties and biocompatibility of UHMWPE-derived materials modified by synchrotron radiation.

PubMed

Bykova, Iu; Weinhardt, V; Kashkarova, A; Lebedev, S; Baumbach, T; Pichugin, V; Zaitsev, K; Khlusov, I

2014-08-01

The applications of synchrotron radiation (SR) in medical imaging have become of great use, particularly in angiography, bronchography, mammography, computed tomography, and X-ray microscopy. Thanks to recently developed phase contrast imaging techniques non-destructive preclinical testing of low absorbing materials such as polymers has become possible. The focus of the present work is characterization and examination of UHMWPE-derived materials widely used in medicine, before and after their exposure to SR during such testing. Physical properties, such as wettability, surface energy, IR-spectroscopy, roughness, optical microscopy, microhardness measurements of UHMWPE samples were studied before and after SR. The relationship between a growth of UHMWPE surface hydrophilicity after SR and surface colonization by stromal cells was studied in vitro. Obtained results demonstrate that SR may be used as prospective direction to examine bulk (porous) structure of polymer materials and/or to modify polymer surface and volume for tissue engineering.

Self-Consistent Field Theories for the Role of Large Length-Scale Architecture in Polymers

NASA Astrophysics Data System (ADS)

Wu, David

At large length-scales, the architecture of polymers can be described by a coarse-grained specification of the distribution of branch points and monomer types within a molecule. This includes molecular topology (e.g., cyclic or branched) as well as distances between branch points or chain ends. Design of large length-scale molecular architecture is appealing because it offers a universal strategy, independent of monomer chemistry, to tune properties. Non-linear analogs of linear chains differ in molecular-scale properties, such as mobility, entanglements, and surface segregation in blends that are well-known to impact rheological, dynamical, thermodynamic and surface properties including adhesion and wetting. We have used Self-Consistent Field (SCF) theories to describe a number of phenomena associated with large length-scale polymer architecture. We have predicted the surface composition profiles of non-linear chains in blends with linear chains. These predictions are in good agreement with experimental results, including from neutron scattering, on a range of well-controlled branched (star, pom-pom and end-branched) and cyclic polymer architectures. Moreover, the theory allows explanation of the segregation and conformations of branched polymers in terms of effective surface potentials acting on the end and branch groups. However, for cyclic chains, which have no end or junction points, a qualitatively different topological mechanism based on conformational entropy drives cyclic chains to a surface, consistent with recent neutron reflectivity experiments. We have also used SCF theory to calculate intramolecular and intermolecular correlations for polymer chains in the bulk, dilute solution, and trapped at a liquid-liquid interface. Predictions of chain swelling in dilute star polymer solutions compare favorably with existing PRISM theory and swelling at an interface helps explain recent measurements of chain mobility at an oil-water interface. In collaboration with: Renfeng Hu, Colorado School of Mines, and Mark Foster, University of Akron. This work was supported by NSF Grants No. CBET- 0730692 and No. CBET-0731319.

Optical and Morphological Properties of P3HT and P3HT: PCBM Thin Films Used in Photovoltaic Applications

NASA Astrophysics Data System (ADS)

Hrostea, L.; Girtan, M.; Mallet, R.; Leontie, L.

2018-06-01

This work is focused on the study of some physical properties of poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly(e-hexylthiophene-2,5-diyl): Methanolfullerene Phenyl-C61-Butyric-Accid-Methyl-Ester (PCBM) blend thin films. Knowing the polymer advantages, such as ease of processing, high thermal stability, strong interaction with light, its properties have captured the attention regarding the changes that can occur in a polymer:fullerene blend in term of them. Polymer and polymer:fullerene blend (1:0.1, 1:0.2, 1:0.4 and 1:0.8 ratios) were deposited by spin coating on glass and SnO2:F (FTO) coated glass. The optical properties were emphasized using spectrophotometry (300 – 2200 nm wavelength range) and spectroscopic ellipsometry models, to obtain the refractive index, extinction coefficient and the transmission (found higher than 80%). According to X-ray diffraction analysis, as-obtained films are amorphous. Investigation of the surface morphology of thin-film samples using Atomic Force Microscopy revealed a crystallite-like surface morphology with crystallite size in the nanometer range.

Bovine serum albumin surface imprinted polymer fabricated by surface grafting copolymerization on zinc oxide rods and its application for protein recognition.

PubMed

Li, Xiangjie; Zhou, Jingjing; Tian, Lei; Li, Wei; Zhang, Baoliang; Zhang, Hepeng; Zhang, Qiuyu

2015-10-01

A novel bovine serum albumin (BSA) surface imprinted polymer based on ZnO rods was synthesized by surface grafting copolymerization. It exhibited an excellent recognition performance to bovine serum albumin. The adsorption capacity and imprinting factor of bovine serum albumin could reach 89.27 mg/g and 2.35, respectively. Furthermore, the fluorescence property of ZnO was used for tracing the process of protein imprinting and it implied the excellent optical sensing property of this material. More importantly, the hypothesis that the surface charge of carrier could affect the imprinting process was confirmed. That is, ZnO with positive surface charge could not only improve the recognition specificity of binding sites to template proteins (pI < 7), but also deteriorate the bindings between sites and non-template proteins (pI > 7). It was also important that the reusability of ZnO@BSA molecularly imprinted polymers was satisfactory. This implied that the poor mechanical/chemical stability of traditional zinc oxide sensors could be solved by the introduction of surface grafting copolymerization. These results revealed that the ZnO@BSA molecularly imprinted polymers are a promising optical/electrochemical sensor element. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cured composite materials for reactive metal battery electrolytes

DOEpatents

Harrup, Mason K.; Stewart, Frederick F.; Peterson, Eric S.

2006-03-07

A solid molecular composite polymer-based electrolyte is made for batteries, wherein silicate compositing produces a electrolytic polymer with a semi-rigid silicate condensate framework, and then mechanical-stabilization by radiation of the outer surface of the composited material is done to form a durable and non-tacky texture on the electrolyte. The preferred ultraviolet radiation produces this desirable outer surface by creating a thin, shallow skin of crosslinked polymer on the composite material. Preferably, a short-duration of low-medium range ultraviolet radiation is used to crosslink the polymers only a short distance into the polymer, so that the properties of the bulk of the polymer and the bulk of the molecular composite material remain unchanged, but the tough and stable skin formed on the outer surface lends durability and processability to the entire composite material product.

Triboelectric energy harvesting with surface-charge-fixed polymer based on ionic liquid

PubMed Central

Sano, Chikako; Mitsuya, Hiroyuki; Ono, Shimpei; Miwa, Kazumoto; Toshiyoshi, Hiroshi; Fujita, Hiroyuki

2018-01-01

Abstract A novel triboelectric energy harvester has been developed using an ionic liquid polymer with cations fixed at the surface. In this report, the fabrication of the device and the characterization of its energy harvesting performance are detailed. An electrical double layer was induced in the ionic liquid polymer precursor to attract the cations to the surface where they are immobilized using a UV-based crosslinking reaction. The finalized polymer is capable of generating an electrical current when contacted by a metal electrode. Using this property, energy harvesting experiments were conducted by cyclically contacting a gold-surface electrode with the charge fixed surface of the polymer. Control experiments verified the effect of immobilizing the cations at the surface. By synthesizing a polymer with the optimal composition ratio of ionic liquid to macromonomer, an output of 77 nW/cm2 was obtained with a load resistance of 1 MΩ at 1 Hz. This tuneable power supply with a μA level current output may contribute to Internet of Things networks requiring numerous sensor nodes at remote places in the environment. PMID:29707070

Determination of elastic mechanical characteristics of surface coatings from analysis of signals obtained by impulse excitation

NASA Astrophysics Data System (ADS)

Nyaguly, E.; Craştiu, I.; Deac, S.; Gozman-Pop, C.; Drăgănescu, G.; Bereteu, L.

2018-01-01

Most of the surface coatings are based on the synthetic polymers, which are substances composed from very large molecules that form tough, flexible, adhesive films when applied to surfaces. The other components of surface coverings materials are pigments that provide colour, opacity, gloss and other properties. Surface coatings are two-phase composite materials: constitute a polymer matrix on the one side, and on the other side of the pigments and additives dispersed in the matrix. Their role is not only aesthetically but also to ensure anticorrosive protection or even improve some mechanical properties of coated surfaces. In this paper it will follow, starting from the mechanical properties of the substrate, the metallic sheet in general, to determine the new properties of the assembly of substrate and the two coating layers, also the determination of mechanical properties of the layers. From the analysis of vibroacoustic signals obtained by the impulse excitation of the sample, one can determine the elasticity modulus. These results come to validate the results based on finite element analysis (FEA) of the same samples.

Catechol-Functionalized Synthetic Polymer as a Dental Adhesive to Contaminated Dentin Surface for a Composite Restoration.

PubMed

Lee, Sang-Bae; González-Cabezas, Carlos; Kim, Kwang-Mahn; Kim, Kyoung-Nam; Kuroda, Kenichi

2015-08-10

This study reports a synthetic polymer functionalized with catechol groups as dental adhesives. We hypothesize that a catechol-functionalized polymer functions as a dental adhesive for wet dentin surfaces, potentially eliminating the complications associated with saliva contamination. We prepared a random copolymer containing catechol and methoxyethyl groups in the side chains. The mechanical and adhesive properties of the polymer to dentin surface in the presence of water and salivary components were determined. It was found that the new polymer combined with an Fe(3+) additive improved bond strength of a commercial dental adhesive to artificial saliva contaminated dentin surface as compared to a control sample without the polymer. Histological analysis of the bonding structures showed no leakage pattern, probably due to the formation of Fe-catechol complexes, which reinforce the bonding structures. Cytotoxicity test showed that the polymers did not inhibit human gingival fibroblast cells proliferation. Results from this study suggest a potential to reduce failure of dental restorations due to saliva contamination using catechol-functionalized polymers as dental adhesives.

Catechol-Functionalized Synthetic Polymer as a Dental Adhesive to Contaminated Dentin Surface for a Composite Restoration

PubMed Central

2015-01-01

This study reports a synthetic polymer functionalized with catechol groups as dental adhesives. We hypothesize that a catechol-functionalized polymer functions as a dental adhesive for wet dentin surfaces, potentially eliminating the complications associated with saliva contamination. We prepared a random copolymer containing catechol and methoxyethyl groups in the side chains. The mechanical and adhesive properties of the polymer to dentin surface in the presence of water and salivary components were determined. It was found that the new polymer combined with an Fe3+ additive improved bond strength of a commercial dental adhesive to artificial saliva contaminated dentin surface as compared to a control sample without the polymer. Histological analysis of the bonding structures showed no leakage pattern, probably due to the formation of Fe–catechol complexes, which reinforce the bonding structures. Cytotoxicity test showed that the polymers did not inhibit human gingival fibroblast cells proliferation. Results from this study suggest a potential to reduce failure of dental restorations due to saliva contamination using catechol-functionalized polymers as dental adhesives. PMID:26176305

Influence of Relative Humidity on AC Corona Discharge from Algae Attached on the Silicone Rubber

NASA Astrophysics Data System (ADS)

Sato, Daisuke; Hara, Yoshiaki; Kokufu, Morihide; Higashiyama, Yoshio

To make clear the influence of algae growth at the surface of a polymer insulator in a practical transmission line, the characteristics of ac corona discharge from an aggregate algae particle were investigated. The aggregate algae particle was made of Protococcus viridis. Corona onset voltage from an aggregate algae particle was decreased as relative humidity increased. Under the condition of relatively higher relative humidity, luminous channel of corona discharge became more strongly and the number of corona pulses in the current waveform was increased. For an aggregate algae particle contaminated with sea salt including MgCl2, corona onset voltage decreased drastically at relative humidity above 40%. This property would result from deliquescence of MgCl2. Corona discharge was strongly affected by existence of MgCl2 in an aggregate algae particle. Surface resistance of algae attached to the surface of the silicone rubber sheet decreased in fourth figures for relative humidity from 20 to 90%. Therefore, the existence of algae on the polymer insulator inevitably affects the electric property and the surface property of the polymer insulator.

Prediction of Elastic Constants of the Fuzzy Fibre Reinforced Polymer Using Computational Micromechanics

NASA Astrophysics Data System (ADS)

Pawlik, Marzena; Lu, Yiling

2018-05-01

Computational micromechanics is a useful tool to predict properties of carbon fibre reinforced polymers. In this paper, a representative volume element (RVE) is used to investigate a fuzzy fibre reinforced polymer. The fuzzy fibre results from the introduction of nanofillers in the fibre surface. The composite being studied contains three phases, namely: the T650 carbon fibre, the carbon nanotubes (CNTs) reinforced interphase and the epoxy resin EPIKOTE 862. CNTs are radially grown on the surface of the carbon fibre, and thus resultant interphase composed of nanotubes and matrix is transversely isotropic. Transversely isotropic properties of the interphase are numerically implemented in the ANSYS FEM software using element orientation command. Obtained numerical predictions are compared with the available analytical models. It is found that the CNTs interphase significantly increased the transverse mechanical properties of the fuzzy fibre reinforced polymer. This extent of enhancement changes monotonically with the carbon fibre volume fraction. This RVE model enables to investigate different orientation of CNTs in the fuzzy fibre model.

Optical and thermal properties in ultrafast laser surface nanostructuring on biodegradable polymer

NASA Astrophysics Data System (ADS)

Yada, Shuhei; Terakawa, Mitsuhiro

2015-03-01

We investigate the effect of optical and thermal properties in laser-induced periodic surface structures (LIPSS) formation on a poly-L-lactic acid (PLLA), a biodegradable polymer. Surface properties of biomaterials are known to be one of the key factors in tissue engineering. Methods to process biomaterial surfaces have been studied widely to enhance cell adhesive and anisotropic properties. LIPSS formation has advantages in a dry processing which is able to process complex-shaped surfaces without using a toxic chemical component. LIPSS, however, was difficult to be formed on PLLA due to its thermal and optical properties compared to other polymers. To obtain new perspectives in effect of these properties above, LIPSS formation dependences on wavelength, pulse duration and repetition rate have been studied. At 800 nm of incident wavelength, high-spatial frequency LIPSS (HSFL) was formed after applying 10000 femtosecond pulses at 1.0 J/cm2 in laser fluence. At 400 nm of the wavelength, HSFL was formed at fluences higher than 0.20 J/cm2 with more than 3000 pulses. Since LIPSS was less formed with lower repetition rate, certain heat accumulation may be required for LIPSS formation. With the pulse duration of 2.0 ps, higher laser fluence as well as number of pulses compared to the case of 120 fs was necessary. This indicates that multiphoton absorption process is essential for LIPSS formation. Study on biodegradation modification was also performed.

Hydroxylation of organic polymer surface: method and application.

PubMed

Yang, Peng; Yang, Wantai

2014-03-26

It may be hardly believable that inert C-H bonds on a polymeric material surface could be quickly and efficiently transformed into C-OH by a simple and mild way. Thanks to the approaches developed recently, it is now possible to transform surface H atoms of a polymeric substrate into monolayer OH groups by a simple/mild photochemical reaction. Herein the method and application of this small-molecular interfacial chemistry is highlighted. The existence of hydroxyl groups on material surfaces not only determines the physical and chemical properties of materials but also provides effective reaction sites for postsynthetic sequential modification to fulfill the requirements of various applications. However, organic synthetic materials based on petroleum, especially polyolefins comprise mainly C and H atoms and thus present serious surface problems due to low surface energy and inertness in reactivity. These limitations make it challenging to perform postsynthetic surface sequential chemical derivatization toward enhanced functionalities and properties and also cause serious interfacial problems when bonding or integrating polymer substrates with natural or inorganic materials. Polymer surface hydroxylation based on direct conversion of C-H bonds on polymer surfaces is thus of significant importance for academic and practical industrial applications. Although highly active research results have reported on small-molecular C-H bond activation in solution (thus homogeneous), most of them, featuring the use of a variety of transition metals as catalysts, present a slow reaction rate, a low atom economy and an obvious environmental pollution. In sharp contrast to these conventional C-H activation strategies, the present Spotlight describes a universal confined photocatalytic oxidation (CPO) system that is able to directly convert polymer surface C-H bonds to C-OSO3(-) and, subsequently, to C-OH through a simple hydrolysis. Generally speaking, these newly implanted hydroxyl groups preserve their own reactivity toward other complementary compounds, thus creating a novel base with distinct surface properties. Thanks to this functionalized platform, a wide range of organic, inorganic and metal materials have been attached to conventional organic polymer substrates through the rational engineering of surface molecular templates from small functional groups to macromolecules. It is expected that the proposed novel CPO method and its versatile usages in advanced material applications will offer new opportunities for a variety of scientific communities, especially for those working on surface/interface modulation.

Mechanical and chemical effects of ion-texturing biomedical polymers

NASA Technical Reports Server (NTRS)

Weigand, A. J.; Cenkus, M. A.

1979-01-01

To determine whether sputter etching may provide substantial polymer surface texturing with insignificant changes in chemical and mechanical properties, an 8 cm beam diameter, electron bombardment, argon ion source was used to sputter etch (ion-texture process) nine biomedical polymers. The materials included silicone rubber, 32% carbon impregnated polyolefin, polyoxymethylene, polytetrafluoroethylene, ultrahigh molecular weight (UHMW) polyethylene, UHMW polyethylene with carbon fibers (10%), and several polyurethanes (bioelectric, segmented, and cross linked). Ion textured microtensile specimens of each material except UHMW polyethylene and UHMW polyethylene with 10% carbon fibers were used to determine the effect of ion texturing on tensile properties. Scanning electron microscopy was used to determine surface morphology changes, and electron spectroscopy for chemical analysis was used to analyze the near surface chemical changes that result from ion texturing. Ion energies of 500 eV with beam current densities ranging from 0.08 to 0.19 mA/sq cm were used to ion texture the various materials. Standard microtensile specimens of seven polymers were exposed to a saline environment for 24 hours prior to and during the tensile testing. The surface chemical changes resulting from sputter etching are minimal in spite of the often significant changes in the surface morphology.

Molecular structures of (3-aminopropyl)trialkoxysilane on hydroxylated barium titanate nanoparticle surfaces induced by different solvents and their effect on electrical properties of barium titanate based polymer nanocomposites

NASA Astrophysics Data System (ADS)

Fan, Yanyan; Wang, Guanyao; Huang, Xingyi; Bu, Jing; Sun, Xiaojin; Jiang, Pingkai

2016-02-01

Surface modification of nanoparticles by grafting silane coupling agents has proven to be a significant approach to improve the interfacial compatibility between inorganic filler and polymer matrix. However, the impact of grafted silane molecular structure after the nanoparticle surface modification, induced by the utilized solvents and the silane alkoxy groups, on the electrical properties of the corresponding nanocomposites, has been seldom investigated. Herein, the silanization on the surface of hydroxylated barium titanate (BT-OH) nanoparticles was introduced by using two kinds of trialkoxysilane, 3-aminopropyltriethoxysilane (AMEO) and 3-aminopropyltrimethoxysilane (AMMO), with different solvents (toluene and ethanol), respectively. Solid-state 13C, 29Si nuclear magnetic resonance (NMR) spectroscopy and high-resolution X-ray photoelectron spectroscopy (XPS) were employed to validate the structure differences of alkoxysilane attachment to the nanoparticles. The effect of alkoxysilane structure attached to the nanoparticle surface on the dielectric properties of the BT based poly(vinylidene fluoride) (PVDF) nanocomposites were investigated. The results reveal that the solvents used for BT nanoparticle surface modification exhibit a significant effect on the breakdown strength of the nanocomposites. Nevertheless, the alkoxy groups of silane show a marginal influence on the dielectric properties of the nanocomposites. These research results provide important insights into the fabrication of advanced polymer nanocomposites for dielectric applications.

Synthesis and characterization of antifouling poly(N-acryloylaminoethoxyethanol) with ultralow protein adsorption and cell attachment.

PubMed

Chen, Hong; Zhang, Mingzhen; Yang, Jintao; Zhao, Chao; Hu, Rundong; Chen, Qiang; Chang, Yung; Zheng, Jie

2014-09-02

Rational design of effective antifouling polymers is challenging but important for many fundamental and applied applications. Herein we synthesize and characterize an N-acryloylaminoethoxyethanol (AAEE) monomer, which integrates three hydrophilic groups of hydroxyl, amide, and ethylene glycol in the same material. AAEE monomers were further grafted and polymerized on gold substrates to form polyAAEE brushes with well-controlled thickness via surface-initiated atomic transfer radical polymerization (SI-ATRP), with particular attention to a better understanding of the molecular structure-antifouling property relationship of hydroxyl-acrylic-based polymers. The surface hydrophilicity and antifouling properties of polyAAEE brushes as a function of film thickness are studied by combined experimental and computational methods including surface plasmon resonance (SPR) sensors, atomic force microscopy (AFM), cell adhesion assay, and molecular dynamics (MD) simulations. With the optimal polymer film thicknesses (∼10-40 nm), polyAAEE-grafted surfaces can effectively resist protein adsorption from single-protein solutions and undiluted human blood plasma and serum to a nonfouling level (i.e., <0.3 ng/cm(2)). The polyAAEE brushes also highly resist mammalian cell attachment up to 3 days. MD simulations confirm that the integration of three hydrophilic groups induce a stronger and closer hydration layer around polyAAEE, revealing a positive relationship between surface hydration and antifouling properties. The molecular structure-antifouling properties relationship of a series of hydroxyl-acrylic-based polymers is also discussed. This work hopefully provides a promising structural motif for the design of new effective antifouling materials beyond traditional ethylene glycol-based antifouling materials.

The Wear Behavior of Textured Steel Sliding against Polymers

PubMed Central

Wang, Meiling; Zhang, Changtao; Wang, Xiaolei

2017-01-01

Artificially fabricated surface textures can significantly improve the friction and wear resistance of a tribological contact. Recently, this surface texturing technique has been applied to polymer materials to improve their tribological performance. However, the wear behavior of textured tribo-pairs made of steel and polymer materials has been less thoroughly investigated and is not well understood; thus, it needs further research. The aim of this study is to investigate the wear properties of tribological contacts made of textured stainless steel against polymer surfaces. Three polymer materials were selected in this study, namely, ultrahigh molecular weight polyethylene (UHMWPE), polyoxymethylene (POM) and (polyetheretherketone) PEEK. Wear tests were operated through a ring-on-plane mode. The results revealed that the texture features and material properties affected the wear rates and friction coefficients of the textured tribo-pairs. In general, PEEK/textured steel achieved the lowest wear rate among the three types of tribo-pairs investigated. Energy dispersive x-ray spectroscopy (EDX) analysis revealed that the elements of C and O on the contacting counterfaces varied with texture features and indicated different wear behavior. Experimental and simulated results showed differences in the stress distribution around the dimple edge, which may influence wear performance. Wear debris with different surface morphologies were found for tribo-pairs with varying texture features. This study has increased the understanding of the wear behavior of tribo-pairs between textured stainless steel and polymer materials. PMID:28772688

Direct laser interference patterning of transparent and colored polymer substrates: ablation, swelling, and the development of a simulation model

NASA Astrophysics Data System (ADS)

Alamri, Sabri; Lasagni, Andrés. F.

2017-02-01

It is well known that micro and sub-micrometer periodical structures play a significant role on the properties of a surface. Ranging from friction reduction to the bacterial adhesion control, the modification of the material surface is the key for improving the performance of a device or even creating a completely new function. Among different laser processing techniques, Direct Laser Interference Patterning (DLIP) relies on the local surface modification process induced when two or more beams interfere and produce periodic surface structures. Although the produced features have controllable pitch and geometry, identical experimental conditions applied to different polymers can result on totally different topologies. In this frame, observations from pigmented and transparent polycarbonate treated with ultraviolet (263 nm) and infrared (1053 nm) laser radiation permitted to identify different phenomena related with the optical and chemical properties of the polymers. As a result from the experimental data analysis, a set of material-dependent constants can be obtained and both profile and surface simulations can be retrieved, reproducing the material surface topography after the surface patterning process.

Polymeric Coatings for Combating Biocorrosion

NASA Astrophysics Data System (ADS)

Guo, Jing; Yuan, Shaojun; Jiang, Wei; Lv, Li; Liang, Bin; Pehkonen, Simo O.

2018-03-01

Biocorrosion has been considered as big trouble in many industries and marine environments due to causing great economic loss. The main disadvantages of present approaches to prevent corrosion include being limited by environmental factors, being expensive, inapplicable to field, and sometimes inefficient. Studies show that polymer coatings with anti-corrosion and anti-microbial properties have been widely accepted as a novel and effective approach to preventbiocorrosion. The main purpose of this review is to summarize up the progressive status of polymer coatings used for combating microbially-induced corrosion. Polymers used to synthesize protective coatings are generally divided into three categories: i) traditional polymers incorporated with biocides, ii) antibacterial polymers containing quaternary ammonium compounds, and iii) conductive polymers. The strategies to synthesize polymer coatings resort mainly to grafting anti-bacterial polymers from the metal substrate surface using novel surface-functionalization approaches, such as free radical polymerization, chemically oxidative polymerization and surface-initiated atom transfer radical polymerization, as opposed to the traditional approaches of dip coating or spin coating.

Preparation Nano-Structure Polytetrafluoroethylene (PTFE) Functional Film on the Cellulose Insulation Polymer and Its Effect on the Breakdown Voltage and Hydrophobicity Properties

PubMed Central

Liu, Cong; Li, Yanqing; Liao, Ruijin; Liao, Qiang; Tang, Chao

2018-01-01

Cellulose insulation polymer is an important component of oil-paper insulation, which is widely used in power transformer. The weight of the cellulose insulation polymer materials is as high as tens of tons in the larger converter transformer. Excellent performance of oil-paper insulation is very important for ensuring the safe operation of larger converter transformer. An effective way to improve the insulation and the physicochemical property of the oil impregnated insulation pressboard/paper is currently a popular research topic. In this paper, the polytetrafluoroethylene (PTFE) functional film was coated on the cellulose insulation pressboard by radio frequency (RF) magnetron sputtering to improve its breakdown voltage and the hydrophobicity properties. X-ray photoelectron spectroscopy (XPS) results show that the nano-structure PTFE functional film was successfully fabricated on the cellulose insulation pressboard surface. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) present that the nanoscale size PTFE particles were attached to the pressboard surface and it exists in the amorphous form. Atomic force microscopy (AFM) shows that the sputtered pressboard surface is still rough. The rough PTFE functional film and the reduction of the hydrophilic hydroxyl of the surface due to the shielding effect of PTFE improve the breakdown and the hydrophobicity properties of the cellulose insulation pressboard obviously. This paper provides an innovative way to improve the performance of the cellulose insulation polymer. PMID:29883376

Preparation Nano-Structure Polytetrafluoroethylene (PTFE) Functional Film on the Cellulose Insulation Polymer and Its Effect on the Breakdown Voltage and Hydrophobicity Properties.

PubMed

Hao, Jian; Liu, Cong; Li, Yanqing; Liao, Ruijin; Liao, Qiang; Tang, Chao

2018-05-21

Cellulose insulation polymer is an important component of oil-paper insulation, which is widely used in power transformer. The weight of the cellulose insulation polymer materials is as high as tens of tons in the larger converter transformer. Excellent performance of oil-paper insulation is very important for ensuring the safe operation of larger converter transformer. An effective way to improve the insulation and the physicochemical property of the oil impregnated insulation pressboard/paper is currently a popular research topic. In this paper, the polytetrafluoroethylene (PTFE) functional film was coated on the cellulose insulation pressboard by radio frequency (RF) magnetron sputtering to improve its breakdown voltage and the hydrophobicity properties. X-ray photoelectron spectroscopy (XPS) results show that the nano-structure PTFE functional film was successfully fabricated on the cellulose insulation pressboard surface. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) present that the nanoscale size PTFE particles were attached to the pressboard surface and it exists in the amorphous form. Atomic force microscopy (AFM) shows that the sputtered pressboard surface is still rough. The rough PTFE functional film and the reduction of the hydrophilic hydroxyl of the surface due to the shielding effect of PTFE improve the breakdown and the hydrophobicity properties of the cellulose insulation pressboard obviously. This paper provides an innovative way to improve the performance of the cellulose insulation polymer.

Some fundamental and applicative properties of [polymer/nano-SiC] hybrid nanocomposites

NASA Astrophysics Data System (ADS)

Kassiba, A.; Bouclé, J.; Makowska-Janusik, M.; Errien, N.

2007-08-01

Hybrid nanocomposites which combine polymer as host matrix and nanocrystals as active elements are promising functional materials for electronics, optics or photonics. In these systems, the physical response is governed by the nanocrystal features (size, surface and defect states), the polymer properties and the polymer-nanocrystal interface. This work reviews some selective nanostructured architectures based on active elements such as silicon carbide (SiC) nanocrystals and polymer host matrices. Beyond an overview of some key properties of the nanocrystals, a main part will be devoted to the electro-optical (EO) properties of SiC based hybrid systems where SiC nanocrystals are embedded in polymer matrices of different chemical nature such as poly-(methylmethacrylate) (PMMA), poly-vinylcarbazole (PVK) or polycarbonate. Using this approach, the organic-inorganic interface effects are emphasised with regard to the dielectric or hole transporting behaviour of PMMA and PVK respectively. These effects are illustrated through different EO responses associated with hybrid composites based on PMMA or PVK.

Mechanical and interfacial properties of poly(vinyl chloride) based composites reinforced by cassava stillage residue with different surface treatments

NASA Astrophysics Data System (ADS)

Zhang, Yanjuan; Gan, Tao; Li, Qian; Su, Jianmei; Lin, Ye; Wei, Yongzuo; Huang, Zuqiang; Yang, Mei

2014-09-01

Cassava stillage residue (CSR), a kind of agro-industrial plant fiber, was modified by coupling agent (CA), mechanical activation (MA), and MA-assisted CA (MACA) surface treatments, respectively. The untreated and different surface treated CSRs were used to prepare plant fibers/polymer composites (PFPC) with poly(vinyl chloride) (PVC) as polymer matrix, and the properties of these CSR/PVC composites were compared. Surface treated CSR/PVC composites possessed better mechanical properties, water resistance and dimensional stability compared with the untreated CSR/PVC composite, attributing to the improvement of interfacial properties between CSR and PVC matrix. MACA-treated CSR was the best reinforcement among four types of CSRs (untreated, MA-treated, CA-treated, and MACA-treated CSRs) because MACA treatment led to the significant improvement of dispersion, interfacial adhesion and compatibility between CSR and PVC. MACA treatment could be considered as an effective and green method for enhancing reinforcement efficiency of plant fibers and the properties of PFPC.

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.

Biofouling on polymeric heat exchanger surfaces with E. coli and native biofilms.

PubMed

Pohl, S; Madzgalla, M; Manz, W; Bart, H J

2015-01-01

The biofouling affinity of different polymeric surfaces (polypropylene, polysulfone, polyethylene terephthalate, and polyether ether ketone) in comparison to stainless steel (SS) was studied for the model bacterium Escherichia coli K12 DSM 498 and native biofilms originating from Rhine water. The biofilm mass deposited on the polymer surfaces was minimized by several magnitudes compared to SS. The cell count and the accumulated biomass of E. coli on the polymer surfaces showed an opposing linear trend. The promising low biofilm formation on the polymers is attributed to the combination of inherent surface properties (roughness, surface energy and hydrophobicity) when compared to SS. The fouling characteristics of E. coli biofilms show good conformity with the more complex native biofilms investigated. The results can be utilized for the development of new polymer heat exchangers when using untreated river water as coolant or for other processes needing antifouling materials.

Fluorinated bottlebrush polymers based on poly(trifluoroethyl methacrylate): Synthesis and characterizations

DOE PAGES

Xu, Yuewen; Wang, Weiyu; Wang, Yangyang; ...

2015-11-25

Bottlebrush polymers are densely grafted polymers with long side-chains attached to a linear polymeric backbone. Their unusual structures endow them with a number of unique and potentially useful properties in solution, in thin films, and in bulk. Despite the many studies of bottlebrushes that have been reported, the structure–property relationships for this class of materials are still poorly understood. In this contribution, we report the synthesis and characterization of fluorinated bottlebrush polymers based on poly(2,2,2-trifluoroethyl methacrylate). The synthesis was achieved by atom transfer radical polymerization (ATRP) using an α-bromoisobutyryl bromide functionalized norbornene initiator, followed by ring-opening metathesis polymerization (ROMP) usingmore » a third generation Grubbs’ catalyst (G3). Rheological characterization revealed that the bottlebrush polymer backbones remained unentangled as indicated by the lack of a rubbery plateau in the modulus. By tuning the size of the backbone of the bottlebrush polymers, near-spherical and elongated particles representing single brush molecular morphologies were observed in a good solvent as evidenced by TEM imaging, suggesting a semi-flexible nature of their backbones in dilute solutions. Thin films of bottlebrush polymers exhibited noticeably higher static water contact angles as compared to that of the macromonomer reaching the hydrophobic regime, where little differences were observed between each bottlebrush polymer. Further investigation by AFM revealed that the surface of the macromonomer film was relatively smooth; in contrast, the surface of bottlebrush polymers displayed certain degrees of nano-scale roughness (R q = 0.8–2.4 nm). The enhanced hydrophobicity of these bottlebrushes likely results from the preferential enrichment of the fluorine containing end groups at the periphery of the molecules and the film surface due to the side chain crowding effect. Furthermore, our results provide key information towards the design of architecturally tailored fluorinated polymers with desirable properties.« less

Phenylethynyl Silsesquioxanes: Monomer Synthesis, Characterization,Thermolysis and Thermal Properties

DTIC Science & Technology

2016-12-14

thermal, mechanical and surface properties of many polymeric systems. A useful analogy is that a POSS is nano-sized particle of silica solubilzed...with organic modifiers (RSiO1.5)n; the organic periphery determines how well the POSS can interact with any host polymer , while the siliceous core adds...various materials affects polymer properties. Herein is reported a synthesis strategy to produce POSS-containing, thermosetting phenylethynyls to yield

Ferritin nanocontainers that self-direct in synthetic polymer systems

NASA Astrophysics Data System (ADS)

Sengonul, Merih C.

Currently, there are many approaches to introduce functionality into synthetic polymers. Among these, for example, are copolymerization, grafting, and blending methods. However, modifications made by such methods also change the thermodynamics and rheological properties of the polymer system of interest, and each new modification often requires a costly reoptimization of polymer processing. Such a reoptimalization would not be necessary if new functionality could be introduced via a container whose external surface is chemically and physically tuned to interact with the parent polymer. The contents of the container could then be changed without changing other important properties of the parent polymer. In this context this thesis project explores an innovative nanocontainer platform which can be introduced into phase-separating homopolymer blends. Ferritin is a naturally existing nanocontainer that can be used synthetically to package and selectively transport functional moieties to a particular phase that is either in the bulk or on the surface of a homopolymer blend system. The principal focus of this work centers on modifying the surface of wild ferritin to: (1) render modified ferritin soluble in a non-aqueous solvent; and (2) impart it with self-directing properties when exposed to a homopolymer blend surface or incorporated into the bulk of a homopolymer blend. Wild ferritin is water soluble, and this research project successfully modified wild ferritin by grafting either amine-functional poly(ethylene glycol) (PEG) or short-chain alkanes to carbodiimide activated carboxylate groups on ferritin's surface. Such modified ferritin is soluble in dichloromethane (DCM). Modification was confirmed by ion-exchange chromatography, zeta-potential measurements, and electrospray mass spectroscopy. FT-IR was used to quantify the extent of PEGylation of the reaction products through area ratios of the -C-O-C asymmetric stretching vibration of the grafted PEG chains to the carbonyl stretching vibration (amide I band) of the protein. The dimensionless grafting density after PEGylation was found to be 0.13 with 120 average grafted PEG chains per ferritin nanocontainer. Modified ferritin was used for bulk modification of a phase-separated polymer blend of poly(desaminotyrosyl tyrosine dodecyl ester carbonate) [PDTD] and PEG. TEM micrographs showed remarkable selectivity of PEGylated ferritin to PEG domains, while alkylated ferritin self-directs to the PDTD matrix. We explain this strong selectivity by the favourable interaction energies between the grafted and free matrix chains. In addition, both modified and wild ferritin were used for surface modification of the phase-separated homopolymer blend of PDTD and poly(ε-caprolactone) (PCL). At physiological pH wild ferritin selectively adsorbed onto the PDTD phase, while alkylated ferritin showed a striking selectivity to PCL phase. We attribute this behavior to the increase in protein's pI point above physiological pH after modification, which changes the electrostatic interactions between the ferritin and the polymer surface. Collectively, these results demonstrate the versatile use of ferritin as a model nanocontainer for the selective modification of surface and bulk properties of polymers.

Preparation and rheological behavior of polymer-modified asphalts

NASA Astrophysics Data System (ADS)

Yousefi, Ali Akbar

1999-09-01

Different materials and methods were used to prepare and stabilize polymer-modified asphalts. Addition of thermoplastic elastomers improved some technically important properties of asphalt. Due to inherent factors like large density difference between asphalt and polyethylene, many physical methods in which the structure of asphalt is unchanged, failed to stabilize this system. The effect of addition of copolymers and a pyrolytic oil residue derived from used tire rubber were also studied and found to be ineffective on the storage stability of the polymer-asphalt emulsions while high and moderate temperature properties of the asphalt were found to be improved. Finally, the technique of catalytic grafting of polymer on the surface of high-density particles (e.g. carbon black) was used to balance the large density difference between asphalt and polymer. The resulting polymer-asphalts were stable at high temperatures and showed enhanced properties at low and high temperatures.

Polymer Brush-Functionalized Chitosan Hydrogels as Antifouling Implant Coatings.

PubMed

Buzzacchera, Irene; Vorobii, Mariia; Kostina, Nina Yu; de Los Santos Pereira, Andres; Riedel, Tomáš; Bruns, Michael; Ogieglo, Wojciech; Möller, Martin; Wilson, Christopher J; Rodriguez-Emmenegger, Cesar

2017-06-12

Implantable sensor devices require coatings that efficiently interface with the tissue environment to mediate biochemical analysis. In this regard, bioinspired polymer hydrogels offer an attractive and abundant source of coating materials. However, upon implantation these materials generally elicit inflammation and the foreign body reaction as a consequence of protein fouling on their surface and concomitant poor hemocompatibility. In this report we investigate a strategy to endow chitosan hydrogel coatings with antifouling properties by the grafting of polymer brushes in a "grafting-from" approach. Chitosan coatings were functionalized with polymer brushes of oligo(ethylene glycol) methyl ether methacrylate and 2-hydroxyethyl methacrylate using photoinduced single electron transfer living radical polymerization and the surfaces were thoroughly characterized by XPS, AFM, water contact angle goniometry, and in situ ellipsometry. The antifouling properties of these new bioinspired hydrogel-brush coatings were investigated by surface plasmon resonance. The influence of the modifications to the chitosan on hemocompatibility was assessed by contacting the surfaces with platelets and leukocytes. The coatings were hydrophilic and reached a thickness of up to 180 nm within 30 min of polymerization. The functionalization of the surface with polymer brushes significantly reduced the protein fouling and eliminated platelet activation and leukocyte adhesion. This methodology offers a facile route to functionalizing implantable sensor systems with antifouling coatings that improve hemocompatibility and pave the way for enhanced device integration in tissue.

Preparation of a bonelike apatite-polymer fiber composite using a simple biomimetic process.

PubMed

Yokoyama, Yoshiro; Oyane, Ayako; Ito, Atsuo

2008-08-01

A bonelike apatite-polymer fiber composite may be useful as an implant material to replace bone, the enthesis of a tendon, and the joint part of a ligament. We treated an ethylene-vinyl alcohol copolymer (EVOH) plate and knitted EVOH fibers with an oxygen plasma to produce oxygen-containing functional groups on their surfaces. The plasma-treated samples were alternately dipped in alcoholic calcium and phosphate ion solutions three times to deposit apatite precursors onto their surfaces. The surface-modified samples formed a dense and uniform bonelike surface apatite layer after immersion for 24 h in a simulated body fluid with ion concentrations approximately equal to those of human blood plasma. The adhesive strength between the apatite layer and the sample's surface increased with increasing power density of the oxygen plasma. The apatite-EVOH fiber composite obtained by our process has similarities to natural bone in that apatite crystals are deposited on organic polymer fibers. The resulting composite would possess osteoconductivity due to the apatite phase. With proper polymer selection and optimized synthesis techniques, a composite could be made that would have bonelike mechanical properties. Hence, the present surface modification and coating process would be a promising route to obtain new implant materials with bonelike mechanical properties and osteoconductivity. (c) 2007 Wiley Periodicals, Inc.

Maximum Frictional Charge Generation on Polymer Surfaces

NASA Astrophysics Data System (ADS)

Calle, Carlos; Groop, Ellen; Mantovani, James; Buehler, Martin

2001-03-01

The maximum amount of charge that a given surface area can hold is limited by the surrounding environmental conditions such as the atmospheric composition, pressure, humidity, and temperature. Above this charge density limit, the surface will discharge to the atmosphere or to a nearby conductive surface that is at a different electric potential. We have performed experiments using the MECA Electrometer, a flight instrument developed jointly by the Jet Propulsion Laboratory and NASA Kennedy Space Center to study the electrostatic properties of the Martian soil. The electrometer contains five types of polymers: fiberglass/epoxy, polycarbonate (Lexan), polytetraflouroethylene (Teflon), Rulon J, and polymethylmethacrylate (PMMA, Lucite). We repeatedly rubbed the polymers with another material until each polymer's charge saturation was determined. We will discuss the correlation of our data with the triboelectric series.

Surface engineering: molecularly imprinted affinity membranes by photograft polymerization

NASA Astrophysics Data System (ADS)

Matuschewski, Heike; Sergeyeva, Tatiana A.; Bendig, Juergen; Piletsky, Sergey A.; Ulbricht, Matthies; Schedler, Uwe

2001-02-01

Commercial polymer microfiltration membranes were surface-modified with a graft copolymer of a functional monomer and a crosslinker in the presence of a template (triazine-herbicide). As result, membranes covered with a thin layer of imprinted polymer (MIP) selective to the template were obtained. The influence of the polymerization conditions on membrane recognition properties was studied by membranes

Photocatalytic activity of PANI loaded coordination polymer composite materials: Photoresponse region extension and quantum yields enhancement via the loading of PANI nanofibers on surface of coordination polymer

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

Cui, Zhongping; Qi, Ji; Xu, Xinxin, E-mail: xuxx@mail.neu.edu.cn

2013-09-15

To enhance photocatalytic property of coordination polymer in visible light region, polyaniline (PANI) loaded coordination polymer photocatalyst was synthesized through in-situ chemical oxidation of aniline on the surface of coordination polymer. The photocatalytic activity of PANI loaded coordination polymer composite material for degradation of Rhodamine B (RhB) was investigated. Compared with pure coordination polymer photocatalyst, which can decompose RhB merely under UV light irradiation, PANI loaded coordination polymer photocatalyst displays more excellent photocatalytic activity in visible light region. Furthermore, PANI loaded coordination polymer photocatalyst exhibits outstanding stability during the degradation of RhB. - Graphical abstract: PANI loaded coordination polymer compositemore » material, which displays excellent photocatalytic activity under visible light was firstly synthesized through in-situ chemical oxidation of aniline on surface of coordination polymer. Display Omitted - Highlights: • This PANI loaded coordination polymer composite material represents the first conductive polymer loaded coordination polymer composite material. • PANI/coordination polymer composite material displays more excellent photocatalytic activity for the degradation of MO in visible light region. • The “combination” of coordination polymer and PANI will enable us to design high-activity, high-stability and visible light driven photocatalyst in the future.« less

Preparing high-density polymer brushes by mechanically assisted polymer assembly (MAPA)

NASA Astrophysics Data System (ADS)

Wu, Tao; Efimenko, Kirill; Genzer, Jan

2001-03-01

We introduce a novel method of modifying the surface properties of materials. This technique, called MAPA (="mechanically assisted polymer assembly"), is based on: 1) chemically attaching polymerization initiators to the surface of an elastomeric network that has been previously stretched by a certain length, Δx, and 2) growing end-anchored macromolecules using surface initiated ("grafting from") atom transfer living radical polymerization. After the polymerization, the strain is removed from the substrate, which returns to its original size causing the grafted macromolecules to stretch away from the substrate and form a dense polymer brush. We demonstrate the feasibility of the MAPA method by preparing high-density polymer brushes of poly(acryl amide), PAAm. We show that, as expected, the grafting density of the PAAm brushes can be increased by increasing Δx. We demonstrate that polymer brushes with extremely high grafting densities can be successfully prepared by MAPA.

Recent Progress on Ferroelectric Polymer-Based Nanocomposites for High Energy Density Capacitors: Synthesis, Dielectric Properties, and Future Aspects.

PubMed

Prateek; Thakur, Vijay Kumar; Gupta, Raju Kumar

2016-04-13

Dielectric polymer nanocomposites are rapidly emerging as novel materials for a number of advanced engineering applications. In this Review, we present a comprehensive review of the use of ferroelectric polymers, especially PVDF and PVDF-based copolymers/blends as potential components in dielectric nanocomposite materials for high energy density capacitor applications. Various parameters like dielectric constant, dielectric loss, breakdown strength, energy density, and flexibility of the polymer nanocomposites have been thoroughly investigated. Fillers with different shapes have been found to cause significant variation in the physical and electrical properties. Generally, one-dimensional and two-dimensional nanofillers with large aspect ratios provide enhanced flexibility versus zero-dimensional fillers. Surface modification of nanomaterials as well as polymers adds flavor to the dielectric properties of the resulting nanocomposites. Nowadays, three-phase nanocomposites with either combination of fillers or polymer matrix help in further improving the dielectric properties as compared to two-phase nanocomposites. Recent research has been focused on altering the dielectric properties of different materials while also maintaining their superior flexibility. Flexible polymer nanocomposites are the best candidates for application in various fields. However, certain challenges still present, which can be solved only by extensive research in this field.

Photoresponsive surface molecularly imprinted polymer on ZnO nanorods for uric acid detection in physiological fluids.

PubMed

Tang, Qian; Li, Zai-Yong; Wei, Yu-Bo; Yang, Xia; Liu, Lan-Tao; Gong, Cheng-Bin; Ma, Xue-Bing; Lam, Michael Hon-Wah; Chow, Cheuk-Fai

2016-09-01

A photoresponsive surface molecularly imprinted polymer for uric acid in physiological fluids was fabricated through a facile and effective method using bio-safe and biocompatible ZnO nanorods as a support. The strategy was carried out by introducing double bonds on the surface of the ZnO nanorods with 3-methacryloxypropyltrimethoxysilane. The surface molecularly imprinted polymer on ZnO nanorods was then prepared by surface polymerization using uric acid as template, water-soluble 5-[(4-(methacryloyloxy)phenyl)diazenyl]isophthalic acid as functional monomer, and triethanolamine trimethacryl ester as cross-linker. The surface molecularly imprinted polymer on ZnO nanorods showed good photoresponsive properties, high recognition ability, and fast binding kinetics toward uric acid, with a dissociation constant of 3.22×10(-5)M in aqueous NaH2PO4 buffer at pH=7.0 and a maximal adsorption capacity of 1.45μmolg(-1). Upon alternate irradiation at 365 and 440nm, the surface molecularly imprinted polymer on ZnO nanorods can quantitatively uptake and release uric acid. Copyright © 2016 Elsevier B.V. All rights reserved.

Studies of Surface Charging of Polymers by Indirect Triboelectrification

NASA Astrophysics Data System (ADS)

Mantovani, James; Calle, Carlos; Groop, Ellen; Buehler, Martin

2001-03-01

Charge is known to develop on the surface of an insulating polymer by frictional charging through direct physical contact with another material. We will present results of recent triboelectrification studies of polymer surfaces that utilized an indirect method of frictional charging. This method first involves placing a grounded thin metal foil in stationary contact over the polymer surface. The exposed metal foil is then rubbed with the surface of the material that generates the triboelectric charge. Data is presented for five types of polymers: fiberglass/epoxy, polycarbonate (Lexan), polytetraflouroethylene (Teflon), Rulon J, and polymethylmethacrylate (PMMA, Lucite). The amount of charge that develops on an insulator's surface is measured using the MECA Electrometer, which was developed jointly by NASA Kennedy Space Center and the Jet Propulsion Laboratory to study the electrostatic properties of soil on the surface of Mars. Even though the insulator's surface is electrically shielded from the rubbing material by the grounded metal foil, charge measurements obtained by the MECA Electrometer after the metal foil is separated from the insulator's surface reveal that the insulator's surface does accumulate charge by indirect frictional charging. A possible explanation of the observations will be presented based on a simple contact barrier model.

Carbon Nanofibers (CNFs) Surface Modification to Fabricate Carbon Nanofibers_Nanopaper Integrated Polymer Composite Material.

PubMed

Jiang, Jianjun; Zhao, Ziwei; Deng, Chao; Liu, Fa; Li, Dejia; Fang, Liangchao; Zhang, Dan; Castro Jose M; Chen, Feng; Lee, L James

2016-06-01

Carbon Nanofibers (CNFs) have shown great potential to improve the physical and mechanical properties of conventional Fiber Reinforced Polymer Composites (FRPCs) surface. Excellent dispersion CNFs into water or polymer matrix was very crucial to get good quality CNFs enhanced FRPCs. Because of the hydrophobic properties of CNFs, we apply the reversible switching principles to transfer the hydrophobic surface into hydrophilic surface by growing polyaniline nanograss on the surface of CNFs which was carried out in hydrochloric acid condition. Incorporating CNFs into FRPCs as a surface layer named CNFs Nanopaper to increase the erosion resistance and electrical conductivity in this research which was very important in the wind energy field. In order to get high quality dispersed CNFs suspension, a sonication unit was used to detangle and uniform disperse the functionalized CNFs. A filter with vacuum pressure used to filter the suspension of CNFs onto Carbon veil to make CNFs Nanopaper. Vacuum Aided Resin Transfer Modeling (VARTM) process was used to fabricate Nano-enhanced FRPCs samples. In order to characterize the mechanical properties, three point bending experiment was measured. The flexural strength capacity and deformation resistance and behavior were compared and analyzed. In this paper, we discussed the methods used and provided experimental parameter and experimental results.

Cicada-Wing-Inspired Self-Cleaning Antireflection Coatings on Polymer Substrates.

PubMed

Chen, Ying-Chu; Huang, Zhe-Sheng; Yang, Hongta

2015-11-18

The cicada has transparent wings with remarkable self-cleaning properties and high transmittance over the whole visible spectral range, which is derived from periodic conical structures covering the wing surface. Here we report a scalable self-assembly technique for fabricating multifunctional optical coatings that mimic cicada-wing structures. Spin-coated two-dimensional non-close-packed colloidal crystals are utilized as etching masks to pattern subwavelength-structured cone arrays directly on polymer substrates. The resulting gratings exhibit broadband antireflection performance and superhydrophobic properties after surface modification. The dependence of the cone shape and size on the antireflective and self-cleaning properties has also been investigated in this study.

Abnormal viscoelastic behavior of side-chain liquid-crystal polymers

NASA Astrophysics Data System (ADS)

Gallani, J. L.; Hilliou, L.; Martinoty, P.; Keller, P.

1994-03-01

We show that, contrary to what is commonly believed, the isotropic phase of side-chain liquid-crystal polymers has viscoelastic properties which are totally different from those of ordinary flexible melt polymers. The results can be explained by the existence of a transient network created by the dynamic association of mesogenic groups belonging to different chains. The extremely high sensitivity of the compound to the state of the surfaces with which it is in contact offers us an unexpected method of studying surface states.

Effect of LEO Exposure on Aromatic Polymers Containing Phenylphosphine Oxide Groups

NASA Technical Reports Server (NTRS)

Watson, K. A.; Ghose, S.; Lillehei, P. T.; Smith, J. G., Jr.; Connell, J. W.

2007-01-01

As part of the Materials on The International Space Station Experiment (MISSE), aromatic polymers containing phenylphosphine oxide groups were exposed to low Earth orbit (LEO) for approximately 4 years. All of the aromatic polymers containing phenylphosphine oxide groups survived the exposure despite the high fluence of atomic oxygen that completely eroded other polymer films such as Kapton and Mylar of comparable or greater thickness. The samples consisted of a colorless polyimide film and a poly(arylene ether benzimidazole) film and thread. The samples were characterized for changes in physical properties, thermal/optical properties (i.e. solar absorptivity and thermal emissivity), surface chemistry (X-ray photoelectron spectroscopy), and surface topography (atomic force microscopy). The data from the polymer samples on MISSE were compared to samples from the same batch of material stored under ambient conditions on Earth. In addition, comparisons were made between the MISSE samples and those subjected to shorter term space flight exposures. The results of these analyses will be presented.

Molecular Level Investigations of Interfacial Friction of Polymer Brush Surfaces

NASA Astrophysics Data System (ADS)

Perry, Scott

2005-03-01

The development of synthetic polymer lubricants to mimic joint lubrication within the human body will be presented. Unlike most industrial applications involving oils and greases, lubrication of these joints is accomplished in an aqueous environment. Fundamentally, water is a poor lubricant in most settings due to the weak pressure dependence of its viscosity, yet the contacting surfaces of skeletal joints function with low friction throughout a lifetime. Motivated by the molecular structure of materials making up joint surfaces, interfacial friction between polymer brush surfaces under aqueous environments has been probed with an array of molecularly sensitive surface analytical techniques including atomic force microscopy. The brush surfaces, comprised of poly(L-lysine)-g-poly(ethylene glycol) (PLL-g-PEG), have been generated through the spontaneous adsorption of polymer from solution onto oxide substrates and sodium borosilicate surfaces (AFM tip). The character of the polymer films has been investigated in-situ with the quartz crystal microbalance (QCM) and atomic force microscope (AFM) and ex-situ with ellipsometry and X-ray photoelectron spectroscopy (XPS). The interfacial friction measurements have been carried out on polymer-coated substrates with bare or polymer-coated, microsphere-attached tips in over a range of solution conditions. It was found that the adsorption of polymer on oxides strikingly reduced the interfacial friction, resulting in ultra-low friction under certain conditions. By using a series of PLL-g-PEG polymers differing from each other in PEG side-chain length and grafting ratio, we observed that frictional properties of polymer-coated interfaces strongly depend on the architecture of PLL-g-PEG. Polymer-film formation and the influence of polymer architecture will be reviewed while the role of solvent and manifestation of ultra-low friction will be discussed in detail.

Zwitterionic polymer functionalization of polysulfone membrane with improved antifouling property and blood compatibility by combination of ATRP and click chemistry.

PubMed

Xiang, Tao; Lu, Ting; Xie, Yi; Zhao, Wei-Feng; Sun, Shu-Dong; Zhao, Chang-Sheng

2016-08-01

The chemical compositions are very important for designing blood-contacting membranes with good antifouling property and blood compatibility. In this study, we propose a method combining ATRP and click chemistry to introduce zwitterionic polymer of poly(sulfobetaine methacrylate) (PSBMA), negatively charged polymers of poly(sodium methacrylate) (PNaMAA) and/or poly(sodium p-styrene sulfonate) (PNaSS), to improve the antifouling property and blood compatibility of polysulfone (PSf) membranes. Attenuated total reflectance-Fourier transform infrared spectra, X-ray photoelectron spectroscopy and water contact angle results confirmed the successful grafting of the functional polymers. The antifouling property and blood compatibility of the modified membranes were systematically investigated. The zwitterionic polymer (PSBMA) grafted membranes showed good resistance to protein adsorption and bacterial adhesion; the negatively charged polymer (PNaSS or PNaMAA) grafted membranes showed improved blood compatibility, especially the anticoagulant property. Moreover, the PSBMA/PNaMAA modified membrane showed both antifouling property and anticoagulant property, and exhibited a synergistic effect in inhibiting blood coagulation. The functionalization of membrane surfaces by a combination of ATRP and click chemistry is demonstrated as an effective route to improve the antifouling property and blood compatibility of membranes in blood-contact. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Relationship between Surface Properties and In Vitro Drug Release from Compressed Matrix Containing Polymeric Materials with Different Hydrophobicity Degrees

PubMed Central

Yarce, Cristhian J.; Echeverri, Juan D.; Palacio, Mario A.; Rivera, Carlos A.; Salamanca, Constain H.

2017-01-01

This work is the continuation of a study focused on establishing relations between surface thermodynamic properties and in vitro release mechanisms using a model drug (ampicillin trihydrate), besides analyzing the granulometric properties of new polymeric materials and thus establishing the potential to be used in the pharmaceutical field as modified delivery excipients. To do this, we used copolymeric materials derived from maleic anhydride with decreasing polarity corresponding to poly(isobutylene-alt-maleic acid) (hydrophilic), sodium salt of poly(maleic acid-alt-octadecene) (amphiphilic), poly(maleic anhydride-alt-octadecene) (hydrophobic) and the reference polymer hydroxyl-propyl-methyl-cellulose (HPMC). Each material alone and in blends underwent spectroscopic characterization by FTIR, thermal characterization by DSC and granulometric characterization using flow and compaction tests. Each tablet was prepared at different polymer ratios of 0%, 10%, 20%, 30% and 40%, and the surface properties were determined, including the roughness by micro-visualization, contact angle and water absorption rate by the sessile drop method and obtaining Wadh and surface free energy (SFE) using the semi-empirical models of Young–Dupré and  Owens-Wendt-Rabel-Käelbe (OWRK), respectively. Dissolution profiles were determined simulating physiological conditions in vitro, where the kinetic models of order-zero, order-one, Higuchi and Korsmeyer–Peppas were evaluated. The results showed a strong relationship between the proportion and nature of the polymer to the surface thermodynamic properties and kinetic release mechanism. PMID:28125020

Blood clearance and biodistribution of polymer brush-afforded silica particles prepared by surface-initiated living radical polymerization.

PubMed

Ohno, Kohji; Akashi, Tatsuki; Tsujii, Yoshinobu; Yamamoto, Masaya; Tabata, Yasuhiko

2012-03-12

The physiological properties of polymer brush-afforded silica particles prepared by surface-initiated living radical polymerization were investigated in terms of the circulation lifetime in the blood and distribution in tissues. Hydrophilic polymers consisting mainly of poly(poly(ethylene glycol) methyl ether methacrylate) were grafted onto silica particles by surface-initiated atom transfer radical polymerization that was mediated by a copper complex to produce hairy hybrid particles. A series of hybrid particles was synthesized by varying the diameter of the silica core and the chain length of the polymer brush to examine the relationship between their physicochemical and physiological properties. The hybrid particles were injected intravenously into mice to investigate systematically their blood clearance and body distribution. It was revealed that the structural features of the hybrid particles significantly affected their in vivo pharmacokinetics. Some hybrid particles exhibited an excellently prolonged circulation lifetime in the blood with a half life of ∼20 h. When such hybrid particles were injected intravenously into a tumor-bearing mouse, they preferentially accumulated in tumor tissue. The tumor-targeted delivery was optically visualized using hybrid particles grafted with fluorescence-labeled polymer brushes.

Temperature-dependent optical properties of gold nanoparticles coated with a charged diblock copolymer and an uncharged triblock copolymer.

PubMed

Volden, Sondre; Kjøniksen, Anna-Lena; Zhu, Kaizheng; Genzer, Jan; Nyström, Bo; Glomm, Wilhelm R

2010-02-23

We demonstrate that the optical properties of gold nanoparticles can be used to detect and follow stimuli-induced changes in adsorbed macromolecules. Specifically, we investigate thermal response of anionic diblock and uncharged triblock copolymers based on poly(N-isopropylacrylamide) (PNIPAAM) blocks adsorbed onto gold nanoparticles and planar gold surfaces in a temperature range between 25 and 60 degrees C. By employing a palette of analytical probes, including UV-visible spectroscopy, dynamic light scattering, fluorescence, and quartz crystal microbalance with dissipation monitoring, we establish that while the anionic copolymer forms monolayers at both low and high temperature, the neutral copolymer adsorbs as a monolayer at low temperatures and forms multilayers above the cloud point (T(C)). Raising the temperature above T(C) severely affects the optical properties of the gold particle/polymer composites, expelling associated water and altering the immediate surroundings of the gold nanoparticles. This effect, stronger for the uncharged polymer, is related to the amount of polymer adsorbed on the surface, where a denser shell influences the surface plasmon band to a greater degree. This is corroborated with light scattering experiments, which reveal that flocculation of the neutral polymer-coated particles occurs at high temperatures. The flocculation behavior of the neutral copolymer on planar gold surfaces results in multilayer formation. The observed effects are discussed within the framework of the Mie-Drude theory.

Antifouling activities of β-cyclodextrin stabilized peg based silver nanocomposites

NASA Astrophysics Data System (ADS)

Punitha, N.; Saravanan, P.; Mohan, R.; Ramesh, P. S.

2017-01-01

Self-polishing polymer composites which release metal biocide in a controlled rate have been widely used in the design of antimicrobial agents and antifouling coatings. The present work focuses on the environmental friendly green synthesis of PEG based SNCs and their application to biocidal activity including marine biofouling. Biocompatible polymer β-CD and adhesive resistance polymer PEG were used to functionalize the SNPs and the as synthesized SNCs exhibit excellent micro fouling activities. The structural and optical properties were confirmed by XRD and UV-visible techniques respectively. The particle surface and cross sectional characteristics were examined by SEM-EDS, HR-TEM, AFM and FTIR. The surface potential was evaluated using ZP analysis and assessment of antibiofouling property was investigated using static immersion method.

Nonlinear optical properties of organic materials V; Proceedings of the 5th Meeting, San Diego, CA, July 22-24, 1992

NASA Astrophysics Data System (ADS)

Williams, David J.

The present volume on nonlinear optical properties of organic materials discusses organic nonlinear optics, polymers for nonlinear optics, characterization of nonlinear properties, photorefractive and second-order materials, harmonic generation in organic materials, and devices and applications. Particular attention is given to organic semiconductor-doped polymer glasses as novel nonlinear media, heterocyclic nonlinear optical materials, loss measurements in electrooptic polymer waveguides, the phase-matched second-harmonic generation in planar waveguides, electrooptic measurements in poled polymers, transient effects in spatial light modulation by nonlinearity-absorbing molecules, the electrooptic effects in organic single crystals, surface acoustic wave propagation in an organic nonlinear optical crystal, nonlinear optics of astaxanthin thin films; and advanced high-temperature polymers for integrated optical waveguides. (No individual items are abstracted in this volume)

Effect of degumming time on silkworm silk fibre for biodegradable polymer composites

NASA Astrophysics Data System (ADS)

Ho, Mei-po; Wang, Hao; Lau, Kin-tak

2012-02-01

Recently, many studies have been conducted on exploitation of natural materials for modern product development and bioengineering applications. Apart from plant-based materials (such as sisal, hemp, jute, bamboo and palm fibre), animal-based fibre is a kind of sustainable natural materials for making novel composites. Silkworm silk fibre extracted from cocoon has been well recognized as a promising material for bio-medical engineering applications because of its superior mechanical and bioresorbable properties. However, when producing silk fibre reinforced biodegradable/bioresorbable polymer composites, hydrophilic sericin has been found to cause poor interfacial bonding with most polymers and thus, it results in affecting the resultant properties of the composites. Besides, sericin layers on fibroin surface may also cause an adverse effect towards biocompatibility and hypersensitivity to silk for implant applications. Therefore, a proper pre-treatment should be done for sericin removal. Degumming is a surface modification process which allows a wide control of the silk fibre's properties, making the silk fibre possible to be used for the development and production of novel bio-composites with unique/specific mechanical and biodegradable properties. In this paper, a cleaner and environmentally friendly surface modification technique for tussah silk in polymer based composites is proposed. The effectiveness of different degumming parameters including degumming time and temperature on tussah silk is discussed through the analyses of their mechanical and morphological properties. Based on results obtained, it was found that the mechanical properties of tussah silk are affected by the degumming time due to the change of the fibre structure and fibroin alignment.

Controlled thermal expansion printed wiring boards based on liquid crystal polymer dielectrics

NASA Technical Reports Server (NTRS)

Knoll, Thomas E.; Blizard, Kent; Jayaraj, K.; Rubin, Leslie S.

1994-01-01

Dielectric materials based on innovative Liquid Crystal Polymers (LCP's) have been used to fabricate surface mount printed wiring boards (PWB's) with a coefficient of thermal expansion matched to leadless ceramic chip carriers. Proprietary and patented polymer processing technology has resulted in self reinforcing material with balanced in-plane mechanical properties. In addition, LCP's possess excellent electrical properties, including a low dielectric constant (less than 2.9) and very low moisture absorption (less than 0.02%). LCP-based multilayer boards processed with conventional drilling and plating processes show improved performance over other materials because they eliminate the surface flatness problems of glass or aramid reinforcements. Laser drilling of blind vias in the LCP dielectric provides a very high density for use in direct chip attach and area array packages. The material is ideally suited for MCM-L and PCMCIA applications fabricated with very thin dielectric layers of the liquid crystal polymer.

Preparation and characterization of polymeric nanocomposite films for application as protective coatings

NASA Astrophysics Data System (ADS)

Gagliardi, S.; Rondino, F.; D'Erme, C.; Persia, F.; Menchini, F.; Santarelli, M. L.; Paulke, B.-R.; Enayati, A. L.; Falconieri, M.

2017-08-01

Addiction of ceramic nanoparticles to acrylic polymers provides a simple and effective means to produce paints with important properties, such as mechanical resistance and tailored wettability, even though for optimal performances, an engineered nanoparticle distribution would be desirable. In this paper we report on the realization and on the morphological and functional characterization of nanocomposites where the nanophase is distributed on the surface of acrylic polymer films, in order to enhance the expression of surface-related properties. To this aim, commercial titanium oxide and silicon oxide nanopowders were dispersed in water and the suspensions were air-sprayed on polymeric films prepared by paint brushing, thus producing a nanostructured ceramic surface coating. Control of the pH of suspensions and acrylic acid functionalization of the surface of titania were used together with high power ultrasonic treatments in order to control dimension of the aggregates in the sprayed suspensions. Optical microscopy, mechanical profilometry, and atomic force microscopy were used to characterize the nanocomposite surface morphology and correlate it to the coating functional properties, evaluated through mechanical abrasion tests and contact angle measurements; also, colorimetry on coated stones was performed in order to test the impact of the coatings on the aesthetical appearance and their photostability under UV irradiation. Results show that the nanostructured ceramic layer slightly improves the resistance of coatings to mechanical abrasion in case of polymer films prepared from latexes. The nanocomposite surface layer does not affect the wettability of the polymer, which remained slightly hydrophilic; this behavior is likely due to inadequate distribution of the nanophase. On the other hand UV-induced superhydrophilicity was observed when the concentration of surface titania nanoparticles is about 0.6 mg/cm2. Colorimetric analysis on historical and Carrara marbles before and after coating evidenced the good transparency of the nanocomposites. Accelerated aging tests permitted to demonstrate that, on the historical marbles, the presence of the nanoparticles has a protective action against UV-induced damage of the underlying polymer film, preventing photodegradation.

Mechanical properties and osteocompatibility of novel biodegradable alanine based polyphosphazenes: Side group effects.

PubMed

Sethuraman, Swaminathan; Nair, Lakshmi S; El-Amin, Saadiq; Nguyen, My-Tien; Singh, Anurima; Krogman, Nick; Greish, Yaser E; Allcock, Harry R; Brown, Paul W; Laurencin, Cato T

2010-06-01

The versatility of polymers for tissue regeneration lies in the feasibility to modulate the physical and biological properties by varying the side groups grafted to the polymers. Biodegradable polyphosphazenes are high-molecular-weight polymers with alternating nitrogen and phosphorus atoms in the backbone. This study is the first of its kind to systematically investigate the effect of side group structure on the compressive strength of novel biodegradable polyphosphazene based polymers as potential materials for tissue regeneration. The alanine polyphosphazene based polymers, poly(bis(ethyl alanato) phosphazene) (PNEA), poly((50% ethyl alanato) (50% methyl phenoxy) phosphazene) (PNEA(50)mPh(50)), poly((50% ethyl alanato) (50% phenyl phenoxy) phosphazene) (PNEA(50)PhPh(50)) were investigated to demonstrate their mechanical properties and osteocompatibility. Results of mechanical testing studies demonstrated that the nature and the ratio of the pendent groups attached to the polymer backbone play a significant role in determining the mechanical properties of the resulting polymer. The compressive strength of PNEA(50)PhPh(50) was significantly higher than poly(lactide-co-glycolide) (85:15 PLAGA) (p<0.05). Additional studies evaluated the cellular response and gene expression of primary rat osteoblast cells on PNEA, PNEA(50)mPh(50) and PNEA(50)PhPh(50) films as candidates for bone tissue engineering applications. Results of the in vitro osteocompatibility evaluation demonstrated that cells adhere, proliferate, and maintain their phenotype when seeded directly on the surface of PNEA, PNEA(50)mPh(50), and PNEA(50)PhPh(50). Moreover, cells on the surface of the polymers expressed type I collagen, alkaline phosphatase, osteocalcin, osteopontin, and bone sialoprotein, which are characteristic genes for osteoblast maturation, differentiation, and mineralization. Copyright 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Mechanical Properties and Osteocompatibility of Novel Biodegradable Alanine Based Polyphosphazenes: Side Group Effects

PubMed Central

Sethuraman, Swaminathan; Nair, Lakshmi S.; El-Amin, Saadiq; Nguyen, My-Tien; Singh, Anurima; Krogman, Nick; Greish, Yaser E.; Allcock, Harry R.; Brown, Paul W.; Laurencin, Cato T.

2010-01-01

The versatility of polymers for tissue regeneration lies in the feasibility to modulate the physical and biological properties by varying the side groups grafted to the polymers. Biodegradable polyphosphazenes are high molecular weight polymers with alternating nitrogen and phosphorus atoms in the backbone. This study is the first of its kind to systematically investigate the effect of side group structure on the compressive strength of novel biodegradable polyphosphazene based polymers as potential materials for tissue regeneration. The alanine polyphosphazene based polymers, poly[bis(ethyl alanato) phosphazene] (PNEA), poly[(50% ethyl alanato) (50% methyl phenoxy) phosphazene] (PNEA50mPh50), poly[(50% ethyl alanato) (50% phenyl phenoxy) phosphazene] (PNEA50PhPh50) where investigated to demonstrate their mechanical properties and osteocompatibility. Results of mechanical testing studies demonstrated the nature and the ratio of the pendent groups attached to the polymer backbone play a significant role in determining the mechanical properties of the resulting polymer. The compressive strength of PNEA50PhPh50 was significantly higher than poly(lactide-co-glycolide) (85:15 PLAGA) (p<0.05). Additional studies evaluated the cellular response and gene expression of primary rat osteoblast cells on PNEA, PNEA50mPh50 and PNEA50PhPh50 films as candidates for bone tissue engineering applications. Results of the in vitro osteocompatibility evaluation demonstrated that cells adhere, proliferate, and maintain their phenotype when seeded directly on the surface of PNEA, PNEA50mPh50, and PNEA50PhPh50 Moreover cells on the surface of the polymers expressed type I collagen, alkaline phosphatase, osteocalcin, osteopontin, and bone sialoprotein which are characteristic genes for osteoblast maturation, differentiation, and mineralization. PMID:20004751

Polymer-encapsulated organic nanoparticles for fluorescence and photoacoustic imaging.

PubMed

Li, Kai; Liu, Bin

2014-09-21

Polymer encapsulated organic nanoparticles have recently attracted increasing attention in the biomedical field because of their unique optical properties, easy fabrication and outstanding performance as imaging and therapeutic agents. Of particular importance is the polymer encapsulated nanoparticles containing conjugated polymers (CP) or fluorogens with aggregation induced emission (AIE) characteristics as the core, which have shown significant advantages in terms of tunable brightness, superb photo- and physical stability, good biocompatibility, potential biodegradability and facile surface functionalization. In this review, we summarize the latest advances in the development of polymer encapsulated CP and AIE fluorogen nanoparticles, including preparation methods, material design and matrix selection, nanoparticle fabrication and surface functionalization for fluorescence and photoacoustic imaging. We also discuss their specific applications in cell labeling, targeted in vitro and in vivo imaging, blood vessel imaging, cell tracing, inflammation monitoring and molecular imaging. We specially focus on strategies to fine-tune the nanoparticle property (e.g. size and fluorescence quantum yield) through precise engineering of the organic cores and careful selection of polymer matrices. The review also highlights the merits and limitations of these nanoparticles as well as strategies used to overcome the limitations. The challenges and perspectives for the future development of polymer encapsulated organic nanoparticles are also discussed.

Effect of surface modification of fibers with a polymer coating on the interlaminar shear strength of a composite and the translation of fiber strength in an F-12 aramid/epoxy composite vessel

NASA Astrophysics Data System (ADS)

Shu-hui, Zhang; Guo-zheng, Liang; Wei, Zhang; Jin-fang, Zeng

2006-11-01

The surface of aramid fibers was modified with a polymer coating — a surface treatment reagent containing epoxy resin. The resulting fibers were examined by using NOL tests, hydroburst tests, and the scanning electron microscopy. The modified fibers had a rougher surface than the untreated ones. The interlaminar shear strength of an aramid-fiber-reinforced epoxy composite was highest when the concentration of polymer coating system was 5%. The translation of fiber strength in an aramid/epoxy composite vessel was improved by 8%. The mechanism of the surface treatment of fibers in improving the mechanical properties of aramid/epoxy composites is discussed.

Factors affecting the sticking of insects on modified aircraft wings

NASA Technical Reports Server (NTRS)

Yi, O.; Chitsaz-Z, M. R.; Eiss, N. S.; Wightman, J. P.

1987-01-01

Past studies have shown that the surface energy of a polymer coating has an important effect on the sticking of insects to the surface. However, mechanical properties of polymer coatings such as elasticity may also be important. A further study is suggested using polymer coatings of known surface energy and modulus so that a better understanding of the mechanism of the sticking of insects to surfaces can be achieved. As the first step for the study, surface analysis and road tests were performed using elastomers having different energies and different moduli. The number of insects sticking to each elastomer was counted and compared from sample to sample and with a control (aluminum). An average height moment was also calculated and comparisons made between samples.

Polymeric membranes: surface modification for minimizing (bio)colloidal fouling.

PubMed

Kochkodan, Victor; Johnson, Daniel J; Hilal, Nidal

2014-04-01

This paper presents an overview on recent developments in surface modification of polymer membranes for reduction of their fouling with biocolloids and organic colloids in pressure driven membrane processes. First, colloidal interactions such as London-van der Waals, electrical, hydration, hydrophobic, steric forces and membrane surface properties such as hydrophilicity, charge and surface roughness, which affect membrane fouling, have been discussed and the main goals of the membrane surface modification for fouling reduction have been outlined. Thereafter the recent studies on reduction of (bio)colloidal of polymer membranes using ultraviolet/redox initiated surface grafting, physical coating/adsorption of a protective layer on the membrane surface, chemical reactions or surface modification of polymer membranes with nanoparticles as well as using of advanced atomic force microscopy to characterize (bio)colloidal fouling have been critically summarized. Copyright © 2013 Elsevier B.V. All rights reserved.

FTIR and Vis-FUV real time spectroscopic ellipsometry studies of polymer surface modifications during ion beam bombardment

NASA Astrophysics Data System (ADS)

Laskarakis, A.; Gravalidis, C.; Logothetidis, S.

2004-02-01

The continuously increasing application of polymeric materials in many scientific and technological fields has motivated an extensive use of polymer surface treatments, which modify the physical and chemical properties of polymer surfaces leading to surface activation and promotion of the surface adhesion. Fourier transform IR spectroscopic ellipsometry (FTIRSE) and phase modulated ellipsometry (PME) in the IR and Vis-FUV spectral regions respectively have been employed for in situ and real time monitoring of the structural changes on the polymer surface obtained by Ar + ion bombardment. The polymers were industrially supplied polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) membranes. The Ar + ion bombardment has found to change the chemical bonding of the films and especially the amount of the CO, C-C and CC groups. The detailed study of the FTIRSE spectra reveals important information about the effect of the Ar + ion bombardment on each of the above bonding groups. Also, the modification of the characteristic features, attributed to electronic transitions in specific bonds of PET and PEN macromolecules, has been studied using PME.

Modification of polycarbonate surface in oxidizing plasma

NASA Astrophysics Data System (ADS)

Ovtsyn, A. A.; Smirnov, S. A.; Shikova, T. G.; Kholodkov, I. V.

2017-11-01

The properties of the surface of the film polycarbonate Lexan 8010 were experimentally studied after treatment in a DC discharge plasma in oxygen and air at pressures of 50-300 Pa and a discharge current of 80 mA. The contact angles of wetting and surface energies are measured. The topography of the surface was investigated by atomic force microscopy. The chemical composition of the surface was determined from the FT-IR spectroscopy data in the variant of total internal reflection, as well as X-ray photoelectron spectroscopy. Treatment in the oxidizing plasma leads to a change in morphology (average roughness increases), an increase in the surface energy, and the concentration of oxygen-containing groups (hydroxyl groups, carbonyl groups in ketones or aldehydes and in oxyketones) on the surface of the polymer. Possible reasons for the difference in surface properties of polymer under the action of oxygen and air plasma on it are discussed.

Flexible Polymer/Metal/Polymer and Polymer/Metal/Inorganic Trilayer Transparent Conducting Thin Film Heaters with Highly Hydrophobic Surface.

PubMed

Kang, Tae-Woon; Kim, Sung Hyun; Kim, Cheol Hwan; Lee, Sang-Mok; Kim, Han-Ki; Park, Jae Seong; Lee, Jae Heung; Yang, Yong Suk; Lee, Sang-Jin

2017-09-27

Polymer/metal/polymer and polymer/metal/inorganic trilayer-structured transparent electrodes with fluorocarbon plasma polymer thin film heaters have been proposed. The polymer/metal/polymer and polymer/metal/inorganic transparent conducting thin films fabricated on a large-area flexible polymer substrate using a continuous roll-to-roll sputtering process show excellent electrical properties and visible-light transmittance. They also exhibit water-repelling surfaces to prevent wetting and to remove contamination. In addition, the adoption of a fluorocarbon/metal/fluorocarbon film permits an outer bending radius as small as 3 mm. These films have a sheet resistance of less than 5 Ω sq -1 , sufficient to drive light-emitting diode circuits. The thin film heater with the fluorocarbon/Ag/SiN x structure exhibits excellent heating characteristics, with a temperature reaching 180 °C under the driving voltage of 13 V. Therefore, the proposed polymer/metal/polymer and polymer/metal/inorganic transparent conducting electrodes using polymer thin films can be applied in flexible and rollable displays as well as automobile window heaters and other devices.

Surface and protective properties of dispersions of film-formers

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

Turishcheva, R.A.; Bakaleinikov, M.B.; Minkina, E.N.

1983-03-01

This article reports on studies of the surface and protective properties of 20% dispersions of film-formers most typically used in film-forming inhibited petroleum-base compositions (FIPC): solid hydrocarbons, fatty acid soaps, asphalt, polymers, natural resins, modified vegetable oils, and an inorganic thickening agent. Investigates the dispersions of Butosil and lithium stearate at respective concentrations of 10% and 8%, in view of the high thickening power of these film-formers. Classifies all of the studied FIPC film-forming components into 2 groups: those wth little thickening effect, a low level of adhesion-cohesion interaction, and a high level of surface and protective properties (the oxidizedmore » solid hydrocarbons and the polymers); and the film-formers that have a large thickening effect, a high level of adhesion-cohesion interaction, and a low level of surface and protective properties (the fatty acid soaps, the solid hydrocarbons, and Butosil). Recommends combining film-formers of both groups in developing new grades of FIPCs.« less

Effect of polymer surface modification on polymer-protein interaction via hydrophilic polymer grafting.

PubMed

Liu, S X; Kim, J-T; Kim, S

2008-04-01

Surface modification of flat sheet ultrafiltration membranes, polyethersulfone (PES), was investigated to improve the hydrophilicity of the membrane surface thereby reducing adsorption of the proteins onto the membrane. Grafting of hydrophilic polymers onto UV/ozone-treated PES was used to improve the hydrophilicity of the commercial PES membranes. Hydrophilic polymers, that is, poly(vinyl alcohol) (PVA), polyethylene glycol (PEG), and chitosan, were employed to graft onto PES membrane surfaces because of their excellent hydrophilic property. The surfaces of modified PES membranes were characterized by contact angle measurement, FTIR, and AFM. The FTIR spectra indicated that PES membranes were successfully modified by grafting of the hydrophilic polymers. The modified PES membranes showed 20% to 50% reduction in contact angle measurements in comparison with those of the virgin PES membrane. The tapping mode AFM technique was employed to investigate the changes of surface topography, cross-section, and root mean square roughness of the modified PES membrane surfaces. The modified PES membranes showed elevated roughness (ranging from 7.0 to 25.7 nm) compared with that of the virgin PES membrane (2.1 nm). It is concluded that grafting of PVA, PEG, or chitosan onto UV/ozone-treated PES membranes increases hydrophilicity and lowers protein adsorption by 20% to 60% compared to the virgin PES membrane. Among the 3 hydrophilic polymers studied, PEG showed the most favorable result in terms of contact angle and protein adsorption.

Polymer Brushes under High Load

PubMed Central

Balko, Suzanne M.; Kreer, Torsten; Costanzo, Philip J.; Patten, Tim E.; Johner, Albert; Kuhl, Tonya L.; Marques, Carlos M.

2013-01-01

Polymer coatings are frequently used to provide repulsive forces between surfaces in solution. After 25 years of design and study, a quantitative model to explain and predict repulsion under strong compression is still lacking. Here, we combine experiments, simulations, and theory to study polymer coatings under high loads and demonstrate a validated model for the repulsive forces, proposing that this universal behavior can be predicted from the polymer solution properties. PMID:23516470

Optical properties of BaTiO3 nanoparticles and silver nanoprisms in polymer host matrices

NASA Astrophysics Data System (ADS)

Requena, Sebastian

Nanocomposites are materials comprised of a host matrix, such as glass or polymer, with embedded nanoparticles. Embedding nanoparticles into the host makes it possible to create materials with properties that are distinctly unique from those of their host and nanoparticle constituents. Nanocomposites can have superior mechanical, thermal, and optical properties compared to their host materials. We characterized the photoluminescent properties of BaTiO3 polymer nanocomposites and the effects of chemically modifying the nanoparticles surface on said properties. BaTiO3 nanopowders of average grain sizes 50 nm and 100 nm were functionalized by (3-aminopropyl)triethoxysilane (3APTS) and mixed with poly(methyl methacrylate)/toluene solution. The nanocomposites films morphology and chemical structure were studied via AFM and FTIR. The photoluminescence spectrum of the pure nanoparticles was composed of an emission at ˜3.0 eV and multiple bands centered at ˜2.5 eV. Surface functionalization of the BaTiO3 nanoparticles via 3APTS increased overall luminescence at room temperature while only enhancing the ˜3.0 eV emission at low-temperature. On the other hand, polymer coating of the functionalized nanoparticles significantly enhances ˜3.0 eV emissions while decreasing emissions associated with near-surface lattice distortions at ˜2.5 eV. Chemical modification of the surface with 3APTS and PMMA presents a pathway to tune and control the photoluminescent properties of BTO nanoparticles. We also present optical studies of two different size distributions of silver triangular nanoprisms, one with a dipole resonance at ˜520 nm and the other with a dipole resonance at ˜650 nm, placed in different media. The silver nanoprisms were embedded in a polyvinyl alcohol (PVA) polymer matrix and oriented by stretching the polymer/nanoprism nanocomposite films. We observe significantly increased linear dichroism in the region associated with the plasmonic in-plane dipole mode upon stretching. Additionally, there is a weaker linear dichroism in the region associated with out-of-plane modes, which vanish in the extinction spectrum of the stretched nanocomposite film. Our results show that these silver nanoprisms are promising as key components in wavelength-specific depolarizers and depolarization-based assays.

Vacuum deposition and curing of liquid monomers

DOEpatents

Affinito, J.D.

1993-11-09

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of standard polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Vacuum deposition and curing of liquid monomers

DOEpatents

Affinito, J.D.

1995-03-07

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of ``standard`` polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Vacuum deposition and curing of liquid monomers

DOEpatents

Affinito, John D.

1993-01-01

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of "standard" polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Vacuum deposition and curing of liquid monomers apparatus

DOEpatents

Affinito, John D.

1996-01-01

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of "standard" polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Vacuum deposition and curing of liquid monomers

DOEpatents

Affinito, John D.

1995-01-01

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of "standard" polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface.

Surface patterning of nanoparticles with polymer patches

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

Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties.more » At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. We demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. Furthermore, these patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.« less

Surface patterning of nanoparticles with polymer patches

DOE PAGES

Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse; ...

2016-08-24

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties.more » At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. We demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. Furthermore, these patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.« less

Surface patterning of nanoparticles with polymer patches

NASA Astrophysics Data System (ADS)

Choueiri, Rachelle M.; Galati, Elizabeth; Thérien-Aubin, Héloïse; Klinkova, Anna; Larin, Egor M.; Querejeta-Fernández, Ana; Han, Lili; Xin, Huolin L.; Gang, Oleg; Zhulina, Ekaterina B.; Rubinstein, Michael; Kumacheva, Eugenia

2016-10-01

Patterning of colloidal particles with chemically or topographically distinct surface domains (patches) has attracted intense research interest. Surface-patterned particles act as colloidal analogues of atoms and molecules, serve as model systems in studies of phase transitions in liquid systems, behave as ‘colloidal surfactants’ and function as templates for the synthesis of hybrid particles. The generation of micrometre- and submicrometre-sized patchy colloids is now efficient, but surface patterning of inorganic colloidal nanoparticles with dimensions of the order of tens of nanometres is uncommon. Such nanoparticles exhibit size- and shape-dependent optical, electronic and magnetic properties, and their assemblies show new collective properties. At present, nanoparticle patterning is limited to the generation of two-patch nanoparticles, and nanoparticles with surface ripples or a ‘raspberry’ surface morphology. Here we demonstrate nanoparticle surface patterning, which utilizes thermodynamically driven segregation of polymer ligands from a uniform polymer brush into surface-pinned micelles following a change in solvent quality. Patch formation is reversible but can be permanently preserved using a photocrosslinking step. The methodology offers the ability to control the dimensions of patches, their spatial distribution and the number of patches per nanoparticle, in agreement with a theoretical model. The versatility of the strategy is demonstrated by patterning nanoparticles with different dimensions, shapes and compositions, tethered with various types of polymers and subjected to different external stimuli. These patchy nanocolloids have potential applications in fundamental research, the self-assembly of nanomaterials, diagnostics, sensing and colloidal stabilization.

``Smart'' Surfaces of Polymer Brushes

NASA Astrophysics Data System (ADS)

Wang, Qiang; Meng, Dong

2009-03-01

``Smart'' surfaces, also known as stimuli-responsive surfaces, can change their properties (e.g., wettability, adhesion, friction, elasticity, and biocompatibility) in response to external stimuli (e.g., temperature, pressure, light, solvent selectivity, ionic strength, type of salt, pH, applied electric field, etc.). In this work, we use numerical self-consistent field calculations to study in detail the structure and stimuli- responses of various polymer brushes, including (1) the thermo- response of PNIPAM brushes in water, (2) solvent-response of uncharged diblock copolymer brushes, and (3) the stimuli- response of charged two-component polymer brushes (including both the binary A/B brushes and diblock copolymer A-B brushes) to ionic strength, pH, and applied electric field. Among the many design parameters (e.g., chain lengths, grafting densities, A-B incompatibility, degree of ionization of charged polymers, etc.) we identify those that strongly affect the surface switchability. Such knowledge is useful to the experimental design of these smart polymer brushes for their applications.

Engineering the Mechanical Properties of Ultrabarrier Films Grown by Atomic Layer Deposition for the Encapsulation of Printed Electronics

DOE PAGES

Bulusu, Anuradha; Singh, Ankit K.; Wang, Cheng-Yin; ...

2015-08-28

Direct deposition of barrier films by atomic layer deposition (ALD) onto printed electronics presents a promising method for packaging devices. Films made by ALD have been shown to possess desired ultrabarrier properties, but face challenges when directly grown onto surfaces with varying composition and topography. Challenges include differing nucleation and growth rates across the surface, stress concentrations from topography and coefficient of thermal expansion (CTE) mismatch, elastic mismatch, and particle contamination that may impact the performance of the ALD barrier. In such cases, a polymer smoothing layer may be needed to coat the surface prior to ALD barrier film deposition.more » We present the impact of architecture on the performance of aluminum oxide (Al2O3)/hafnium oxide (HfO2) ALD nanolaminate barrier films deposited on fluorinated polymer layer using an optical calcium (Ca) test under damp heat. It is found that with increasing polymer thickness, the barrier films with residual tensile stress are prone to cracking resulting in rapid failure of the Ca sensor at 50{degree sign}C/85% RH. Inserting a SiNx layer with residual compressive stress between the polymer and ALD layers is found to prevent cracking over a range of polymer thicknesses with more than 95% of the Ca sensor remaining after 500 h of testing. These results suggest that controlling mechanical properties and film architecture play an important role in the performance of direct deposited ALD barriers.« less

Improvement of mechanical robustness of the superhydrophobic wood surface by coating PVA/SiO2 composite polymer

NASA Astrophysics Data System (ADS)

Liu, Feng; Wang, Shuliang; Zhang, Ming; Ma, Miaolian; Wang, Chengyu; Li, Jian

2013-09-01

Improvement of the robustness of superhydrophobic surfaces is crucial for the purpose of achieving commercial applications of these surfaces in such various areas as self-cleaning, water repellency and corrosion resistance. We have investigated a fabrication of polyvinyl alcohol (PVA)/silica (SiO2) composite polymer coating on wooden substrates with super repellency toward water, low sliding angles, low contact angle hysteresis, and relatively better mechanical robustness. The composite polymer slurry, consisting of well-mixing SiO2 particles and PVA, is prepared simply and subsequently coated over wooden substrates with good adhesion. In this study, the mechanical robustness of superhydrophobic wood surfaces was evaluated. The effect of petaloid structures of the composite polymer on robustness was investigated using an abrasion test and the results were compared with those of superhydrophobic wood surfaces fabricated by other processes. The produced wood surfaces exhibited promising superhydrophobic properties with a contact angle of 159̊ and a sliding angle of 4̊, and the relatively better mechanical robustness.

Real-time monitoring of surface-initiated atom transfer radical polymerization using silicon photonic microring resonators: implications for combinatorial screening of polymer brush growth conditions.

PubMed

Limpoco, F Ted; Bailey, Ryan C

2011-09-28

We directly monitor in parallel and in real time the temporal profiles of polymer brushes simultaneously grown via multiple ATRP reaction conditions on a single substrate using arrays of silicon photonic microring resonators. In addition to probing relative polymerization rates, we show the ability to evaluate the dynamic properties of the in situ grown polymers. This presents a powerful new platform for studying modified interfaces that may allow for the combinatorial optimization of surface-initiated polymerization conditions.

Polymer/Carbon-Based Hybrid Aerogels: Preparation, Properties and Applications

PubMed Central

Zuo, Lizeng; Zhang, Youfang; Zhang, Longsheng; Miao, Yue-E; Fan, Wei; Liu, Tianxi

2015-01-01

Aerogels are synthetic porous materials derived from sol-gel materials in which the liquid component has been replaced with gas to leave intact solid nanostructures without pore collapse. Recently, aerogels based on natural or synthetic polymers, called polymer or organic aerogels, have been widely explored due to their porous structures and unique properties, such as high specific surface area, low density, low thermal conductivity and dielectric constant. This paper gives a comprehensive review about the most recent progresses in preparation, structures and properties of polymer and their derived carbon-based aerogels, as well as their potential applications in various fields including energy storage, adsorption, thermal insulation and flame retardancy. To facilitate further research and development, the technical challenges are discussed, and several future research directions are also suggested in this review. PMID:28793602

Modification of surface properties of cellulosic substrates by quaternized silicone emulsions.

PubMed

Purohit, Parag S; Somasundaran, P

2014-07-15

The present work describes the effect of quaternization of silicones as well as the relevant treatment parameter pH on the frictional, morphological and relaxation properties of fabric substrates. Due to their unique surface properties, silicone polymers are extensively used to modify surface properties of various materials, although the effects of functionalization of silicones and relevant process conditions on modification of substrates are not well understood. Specifically we show a considerable reduction in fabric friction, roughness and waviness upon treatment with quaternized silicones. The treatment at acidic pH results in better deposition of silicone polymers onto the fabric as confirmed through streaming potential measurements which show charge reversal of the fabric. Interestingly, Raman spectroscopy studies show the band of C-O ring stretching mode at ∼1095 cm(-1) shift towards higher wavenumber indicating lowering of stress in fibers upon appropriate silicone treatment. Thus along with the morphological and frictional properties being altered, silicone treatment can lead to a reduction in fabric strain. It is concluded that the electrostatic interactions play an initial role in modification of the fiber substrate followed by multilayer deposition of polymer. This multi-technique approach to study fiber properties upon treatment by combining macro to molecular level methods has helped in understanding of new functional coating materials. Copyright © 2014 Elsevier Inc. All rights reserved.

Structure-induced switching of interpolymer adhesion at a solid-polymer melt interface.

PubMed

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo; Chen, Zhizhao; Cheung, Justin M; Morimitsu, Yuma; Endoh, Maya K; Koga, Tadanori; Fukuto, Masafumi; Yuan, Guangcui; Satija, Sushil K; Carrillo, Jan-Michael Y; Sumpter, Bobby G

2018-02-14

Here we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: "flattened chains" which lie flat on the solid and are densely packed, and "loosely adsorbed polymer chains" which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer-adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as "connector molecules", bridging the free chains and substrate surface and improving the interfacial adhesion. These findings not only shed light on the structure-property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.

Review paper: progress in the field of conducting polymers for tissue engineering applications.

PubMed

Bendrea, Anca-Dana; Cianga, Luminita; Cianga, Ioan

2011-07-01

This review focuses on one of the most exciting applications area of conjugated conducting polymers, which is tissue engineering. Strategies used for the biocompatibility improvement of this class of polymers (including biomolecules' entrapment or covalent grafting) and also the integrated novel technologies for smart scaffolds generation such as micropatterning, electrospinning, self-assembling are emphasized. These processing alternatives afford the electroconducting polymers nanostructures, the most appropriate forms of the materials that closely mimic the critical features of the natural extracellular matrix. Due to their capability to electronically control a range of physical and chemical properties, conducting polymers such as polyaniline, polypyrrole, and polythiophene and/or their derivatives and composites provide compatible substrates which promote cell growth, adhesion, and proliferation at the polymer-tissue interface through electrical stimulation. The activities of different types of cells on these materials are also presented in detail. Specific cell responses depend on polymers surface characteristics like roughness, surface free energy, topography, chemistry, charge, and other properties as electrical conductivity or mechanical actuation, which depend on the employed synthesis conditions. The biological functions of cells can be dramatically enhanced by biomaterials with controlled organizations at the nanometer scale and in the case of conducting polymers, by the electrical stimulation. The advantages of using biocompatible nanostructures of conducting polymers (nanofibers, nanotubes, nanoparticles, and nanofilaments) in tissue engineering are also highlighted.

Biomimicry 1: PC.

PubMed

Cumberland, D C; Gunn, J; Malik, N; Holt, C M

1998-01-01

The surface properties of stents can be modified by coating them, for example with a polymer. Phosphorylcoline (PC) is the major component of the outer layer of the cell membrane. The haemo- and biocompatibility of a PC-containing polymer is thus based on biomimicry, and has been confirmed by several experiments showing much reduced thrombogenicity of PC-coated surfaces, and porcine coronary artery implants showing no sign of adverse effect. Clinical experience with the PC-coated BiodivYsio appears favourable. The PC coating can be tailored for take up and controlled elution of various drugs for stent-based local delivery, a property which is being actively explored.

Effects of rare earth oxide additive on surface and tribological properties of polyimide composites

NASA Astrophysics Data System (ADS)

Pan, Zihe; Wang, Tianchang; Chen, Li; Idziak, Stefan; Huang, Zhaohui; Zhao, Boxin

2017-09-01

Rare earth oxide La2O3 microparticles-reinforced polyimide (PI) composites (La-PI-Cs) were fabricated, aiming to improve the tribological property of PI. Surface roughness, surface composition, bulk structure, friction force (Ff) and coefficient of friction (COF) at macro/micro preload, and anti-wear performances of La-PI-Cs were studied and compared with neat PI. With La2O3 microparticles, La-PI-Cs showed larger surface roughness, lower surface energy, and higher hydrophobicity than neat PI, and displayed beneficial layered structure different from the compact structure of PI. Owing to these advantages, La-PI-Cs were found to show a 70% reduction in Ff and COF, and a 30% reduction in wear rate, indicating significantly lowered friction and enhanced anti-wear properties after adding La2O3 microparticles. Our research findings demonstrated an easy and low cost method to fabricate polymer composites with low friction and high wear resistance, and help meet the demanding of polymer composites with high tribological performances in broaden applications.

Mechanism of the dielectric enhancement in polymer-alumina nano-particle composites

NASA Astrophysics Data System (ADS)

Jacob, Rebecca; Jacob, Anne Pavitra; Mainwaring, David E.

2009-09-01

Polymer-alumina nano-composites with enhanced dielectric properties as a possibility to enable the miniaturization of devices have been reported. The enhancement of dielectric properties was found to be unique to the polymer. In the present work, the mechanism of the dielectric enhancement is established by performing ab initio molecular orbital calculations in order to study the molecular interactions in the interfacial region between the alumina-nano-particle surface and the polymer medium. The calculations predict the existence of strong electrostatic attraction between the positive charge on the aluminium of the alumina clusters and the negative charge of the oxygens of the polymer at the polymer-nano-particle interface resulting in an increase in the dipole moment and the polarization of the system leading to enhanced dielectric properties. The oxygen thus plays a dual role by involving in covalent bonding with the polymer chain and electrostatic bonding interactions with the alumina nano-particles. The unique structure of the polymer provides the highly electronegative oxygens, as carbonyl groups or ether linkages in conjugation with aromatic rings in an extended polymer chain system, facilitating this type of bonding at the interface.

Catalyst-free "click" functionalization of polymer brushes preserves antifouling properties enabling detection in blood plasma.

PubMed

Parrillo, Viviana; de Los Santos Pereira, Andres; Riedel, Tomas; Rodriguez-Emmenegger, Cesar

2017-06-08

Progress in biosensors for clinical detection critically relies on modifications of the transducer surface to prevent non-specific adsorption from matrix components (i.e. antifouling) while supporting biomolecular recognition elements to capture the analyte. Such combination of properties presents a significant challenge. Hierarchically structured polymer brushes comprising an antifouling polymer bottom block and a functionalizable top block are proposed as a promising strategy to achieve this goal. We employed the catalyst-free strain-promoted alkyne-azide cycloaddition (SPAAC) "click" reaction to biofunctionalize antifouling polymer brushes without impairing their resistance to fouling. The functionalization was performed on the side chains along the top polymer block or only on the end-groups of the polymer brush. The immobilized amounts of bioreceptors (streptavidin followed by biotin-conjugated proteins) and the resistance to fouling from blood plasma of the surfaces obtained were evaluated via surface plasmon resonance. The end group functionalization approach resulted in very low immobilization of bioreceptor. On the other hand, the side group modification of a top polymer block led to immobilization of 83% of a monolayer of streptavidin. Following binding of a biotin-conjugated antibody (66 ng cm -2 ) the functionalized layer was able to reduce the fouling from undiluted human blood plasma by 89% in comparison with bare gold. Finally, the functionalized hierarchical polymer brushes were applied to the label-free detection of a model analyte in diluted human blood plasma, highlighting the potential for translation to medical applications. Copyright © 2017. Published by Elsevier B.V.

Facile surface modification of glass with zwitterionic polymers for improving the blood compatibility

NASA Astrophysics Data System (ADS)

Zhang, Lingling; Chen, Xiaojuan; Liu, Pingsheng; Wang, Jing; Zhu, Haomiao; Li, Li

2018-06-01

A facile procedure to modify glass film with zwitterionic polymers for improving the blood compatibility was introduced. The glass slides were first silanized with 3-methacryloxypropyltrimethoxysilane (MPT) to generate methacrylate groups on the surface. Then, N, N’-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl) ammonium (DMMSA), a sulfobetaine zwitterionic monomer, was polymerized on the silanized glass substrates by free-radical polymerization in order to graft the zwitterionic polymers onto the substrates. X-ray Photoelectron Spectroscopy (XPS), water contact angle, scanning electron microscope (SEM) and atomic force microscopy (AFM) were utilized to analyze the surface properties of the grafted glass. The blood compatibility of the grafted glass was verified by whole blood contacting and platelet adhesion experiments in vitro. The results showed that the zwitterionic polymers were successfully grafted on the glass surface, and consequently significantly inhibited the platelet adhesion and whole blood cell attachment.

Influence of polymer architecture on antigens camouflage, CD47 protection and complement mediated lysis of surface grafted red blood cells.

PubMed

Chapanian, Rafi; Constantinescu, Iren; Rossi, Nicholas A A; Medvedev, Nadia; Brooks, Donald E; Scott, Mark D; Kizhakkedathu, Jayachandran N

2012-11-01

Hyperbranched polyglycerol (HPG) and polyethylene glycol (PEG) polymers with similar hydrodynamic sizes in solution were grafted to red blood cells (RBCs) to investigate the impact of polymer architecture on the cell structure and function. The hydrodynamic sizes of polymers were calculated from the diffusion coefficients measured by pulsed field gradient NMR. The hydration of the HPG and PEG was determined by differential scanning calorimetry analyses. RBCs grafted with linear PEG had different properties compared to the compact HPG grafted RBCs. HPG grafted RBCs showed much higher electrophoretic mobility values than PEG grafted RBCs at similar grafting concentrations and hydrodynamic sizes indicating differences in the structure of the polymer exclusion layer on the cell surface. PEG grafting impacted the deformation properties of the membrane to a greater degree than HPG. The complement mediated lysis of the grafted RBCs was dependent on the type of polymer, grafting concentration and molecular size of grafted chains. At higher molecular weights and graft concentrations both HPG and PEG triggered complement activation. The magnitude of activation was higher with HPG possibly due to the presence of many hydroxyl groups per molecule. HPG grafted RBCs showed significantly higher levels of CD47 self-protein accessibility than PEG grafted RBCs at all grafting concentrations and molecular sizes. PEG grafted polymers provided, in general, a better shielding and protection to ABO and minor antigens from antibody recognition than HPG polymers, however, the compact HPGs provided greater protection of certain antigens on the RBC surface. Our data showed that HPG 20 kDa and HPG 60 kDa grafted RBCs exhibited properties that are more comparable to the native RBC than PEG 5 kDa and PEG 10 kDa grafted RBCs of comparable hydrodynamic sizes. The study shows that small compact polymers such as HPG 20 kDa have a greater potential in the generation of functional RBC for therapeutic delivery applications. The intermediate sized polymers (PEG or HPG) which showed greater antigen camouflage at lower grafting concentrations have significant potential in transfusion as universal red blood donor cells. Copyright © 2012 Elsevier Ltd. All rights reserved.

Interfacial properties of hydrosoluble polymers. Final report, June 15, 1993--June 15, 1996

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

NONE

1996-12-31

During this period, the authors treated a myriad of problems associated with the interfacial properties of macromolecules. Many of them concerned indirect interactions between surfaces engendered by intervening species. The issues ranged from colloidal forces to membrane induced coupling between embedded macromolecules (membrane-bound proteins). This report presents summaries of the following papers published as a result of this study: membrane interactions with polymers and colloids; escape transitions and force laws for compressed polymer mushrooms; interaction between finite-sized particles and end grafted polymers; one long chain among shorter chains--the Flory approach revisited; conformation of star polymers in high molecular weight solvents;more » membrane-induced interactions between inclusions; filled polymer brushes--a hydrodynamic analogy; polymer adsorption at liquid/air interfaces under lateral pressure; flow induced instability of the interface between a fluid and a gel at low Reynolds number; and fluctuation-induced forces in stacked fluid membranes.« less

Development of a novel test-setup for identifying the frictional characteristics of carbon fibre reinforced polymer composites at high surface pressure

NASA Astrophysics Data System (ADS)

Saxena, Prateek; Schinzel, Marie; Andrich, Manuela; Modler, Niels

2016-09-01

Carbon fibre reinforced polymer composites are extensively used in industrial applications. They are light in weight and have excellent load bearing properties. To understand this material's behaviour when carrying loads at high pressure, a tensile-friction test device was developed that can apply a contact surface pressure between composite and counterpart of 50-300 MPa. A tribological investigation of carbon fibre reinforced epoxy composites was carried out, in which the influence of the surface morphology was investigated by using grinding and sandblasting techniques. The friction coefficient of the polymer composite was measured at 100 MPa surface pressure against uncoated and Diamond-Like Carbon coated stainless steel counterparts.

Structural and elastic properties and stability characteristics of oxygenated carbon nanotubes under physical adsorption of polymers

NASA Astrophysics Data System (ADS)

Ansari, R.; Ajori, S.; Rouhi, S.

2015-03-01

The importance of covalent and non-covalent functionalization approaches for modification the properties of carbon nanotubes is being more widely recognized. To this end, elastic properties and buckling behavior of oxygenated CNT with atomic oxygen and hydroxyl under physical adsorption of PE (Polyethylene) and PEO (Poly (ethylene oxide)) are determined through employing the molecular dynamics (MD) simulations. The results demonstrate that non-covalent bonding of polymer on the surface of oxygenated CNT causes reductions in the variations of critical buckling load and critical strain compared to oxygenated CNTs. Critical buckling load and critical strain of oxygenated CNT/polymer are higher than those of oxygenated CNT. Also, it is demonstrated that critical buckling load and critical strain values in the case of oxygenated CNT/polymer are independent of polymer type unlike the value of Young's modulus. It is shown that variations of Young's modulus decrease as PE adsorbed on the surface of oxygenated CNT. Moreover, the presence of oxygen atom on PEO chain leads to bigger variations of Young's modulus with weight percentage of chemisorbed component, i.e. atomic oxygen and hydroxyl. It is also demonstrated that Young's modulus reduces more considerably in the presence of PEO chain compared to PE one.

Synthesis and Physical Properties of Poly(Perfluoroalkylether)Urethanes

DTIC Science & Technology

1989-05-30

Differential scanning calorimetry and dynamic mechanical analysis showed that the incorporation of PFEG into the soft segment phase slightly enhanced...for all the polymers, using electron spectroscopy for chemical analysis (ESCA). The dynamic contact angle results indicate that the polymer surfaces...these polymers were evaluated by a variety of techniques. Differential scanning calorimetry and dynamic mechanical analysis showed that the

Synthesis and Transport Properties of Novel MOF/PIM-1/MOF Sandwich Membranes for Gas Separation

PubMed Central

Fuoco, Alessio; Khdhayyer, Muhanned R.; Attfield, Martin P.; Esposito, Elisa; Jansen, Johannes C.; Budd, Peter M.

2017-01-01

Metal-organic frameworks (MOFs) were supported on polymer membrane substrates for the fabrication of composite polymer membranes based on unmodified and modified polymer of intrinsic microporosity (PIM-1). Layers of two different MOFs, zeolitic imidazolate framework-8 (ZIF-8) and Copper benzene tricarboxylate ((HKUST-1), were grown onto neat PIM-1, amide surface-modified PIM-1 and hexamethylenediamine (HMDA) -modified PIM-1. The surface-grown crystalline MOFs were characterized by a combination of several techniques, including powder X-ray diffraction, infrared spectroscopy and scanning electron microscopy to investigate the film morphology on the neat and modified PIM-1 membranes. The pure gas permeabilities of He, H2, O2, N2, CH4, CO2 were studied to understand the effect of the surface modification on the basic transport properties and evaluate the potential use of these membranes for industrially relevant gas separations. The pure gas transport was discussed in terms of permeability and selectivity, highlighting the effect of the MOF growth on the diffusion coefficients of the gas in the new composite polymer membranes. The results confirm that the growth of MOFs on polymer membranes can enhance the selectivity of the appropriately functionalized PIM-1, without a dramatic decrease of the permeability. PMID:28208658

Fabrication of transition metal-containing nanostructures via polymer templates for a multitude of applications

NASA Astrophysics Data System (ADS)

Lu, Jennifer Qing

Nanostructures such as carbon nanotubes and semiconducting nanowires offer great technological promise due to their remarkable properties. The lack of a rational synthesis method prevents fabricating these nanostructures with desirable and consistent properties at predefined locations for device applications. In this thesis, employing polymer templates, a variety of highly ordered catalytically active transition metal nanostructures, ranging from single metallic nanoparticles of Fe, Co, Ni, Au and bimetallic nanoparticles of Ni/Fe and Co/Mo to Fe-rich silicon oxide nanodomains with uniform and tunable size and spacing have been successfully synthesized. These nanostructures have been demonstrated to be excellent catalyst systems for the synthesis of carbon nanotube and silicon nanowire. High quality, small diameter carbon nanotubes and nanowires with narrow size distribution have been successfully attained. Because these catalytically active nanostructures are uniformly distributed and do not agglomerate at the growth temperatures, uniform, high density and high quality carbon nanotube mats have been obtained. Since this polymer template approach is fully compatible with conventional top-down photolithography, lithographically selective growth of carbon nanotubes on a surface or suspended carbon nanotubes across trenches have been produced by using existing semiconductor processing. We have also shown the feasibility of producing carbon nanotubes and silicon nanowires at predefined locations on a wafer format and established a wafer-level carbon nanotube based device fabrication process. The ability of the polymer template approach to control catalyst systems at the nano-, micro- and macro-scales paves a pathway for commercialization of these 1D nanostructure-enabled devices. Beside producing well-defined, highly ordered discrete catalytically active metal-containing nanostructures by the polymer template approach, Au and Ag nanotextured surfaces have also been attained by using a self-assembled ferrocenylsilane-based inorganic block copolymer template. These Au and Ag nanotextured surfaces exhibit different surface plasmon behavior than the nanotextured surface. Greatly enhanced and uniform Raman scattering have been observed on Ag nanotextured surfaces. Highly sensitive Au nanotextured surfaces suggest their potential application as sensing surfaces for SPR-based biodetection. This simple fabrication technique of producing inorganic nanostructures with adjustable properties such as size, spacing and composition offers great promise for both fundamental research and technological development.

Polymer Stress-Gradient Induced Migration in Thin Film Flow Over Topography

NASA Astrophysics Data System (ADS)

Tsouka, Sophia; Dimakopoulos, Yiannis; Tsamopoulos, John

2014-11-01

We consider the 2D, steady film flow of a dilute polymer solution over a periodic topography. We examine how the distribution of polymer in the planarization of topographical features is affected by flow intensity and physical properties. The thermodynamically acceptable, Mavrantzas-Beris two-fluid Hamiltonian model is used for polymer migration. The resulting system of differential equations is solved via the mixed FE method combined with an elliptic grid generation scheme. We present numerical results for polymer concentration, stress, velocity and flux of components as a function of the non-dimensional parameters of the problem (Deborah, Peclet, Reynolds and Capillary numbers, ratio of solvent viscosity to total liquid viscosity and geometric features of the topography). Polymer migration to the free surface is enhanced when the cavity gets steeper and deeper. This increases the spatial extent of the polymer depletion layer and induces strong banding in the stresses away from the substrate wall, especially in low polymer concentration. Macromolecules with longer relaxation times are predicted to migrate towards the free surface more easily, while high surface tension combined with a certain range of Reynolds numbers affects the free surface deformations. Work supported by the General Secretariat of Research & Technology of Greece through the program ``Excellence'' (Grant No. 1918) in the framework ``Education and Lifelong Learning'' co-funded by the ESF.

Application of modern surface analytical tools in the investigation of surface deterioration processes

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1983-01-01

Surface profilometry and scanning electron microscopy were utilized to study changes in the surface of polymers when eroded. The X-ray photoelectron spectroscopy (XPS) and depth profile analysis indicate the corrosion of metal and ceramic surfaces and reveal the diffusion of certain species into the surface to produce a change in mechanical properties. Ion implantation, nitriding and plating and their effects on the surface are characterized. Auger spectroscopy analysis identified morphological properties of coatings applied to surfaces by sputter deposition.

Surface modification and characterization of indium-tin oxide for organic light-emitting devices.

PubMed

Zhong, Z Y; Jiang, Y D

2006-10-15

In this work, we used different treatment methods (ultrasonic degreasing, hydrochloric acid treatment, and oxygen plasma) to modify the surfaces of indium-tin oxide (ITO) substrates for organic light-emitting devices. The surface properties of treated ITO substrates were studied by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), sheet resistance, contact angle, and surface energy measurements. Experimental results show that the ITO surface properties are closely related to the treatment methods, and the oxygen plasma is more efficient than the other treatments since it brings about smoother surfaces, lower sheet resistance, higher work function, and higher surface energy and polarity of the ITO substrate. Moreover, polymer light-emitting electrochemical cells (PLECs) with differently treated ITO substrates as device electrodes were fabricated and characterized. It is found that surface treatments of ITO substrates have a certain degree of influence upon the injection current, brightness, and efficiency, but hardly upon the turn-on voltages of current injection and light emission, which are in agreement with the measured optical energy gap of the electroluminescent polymer. The oxygen plasma treatment on the ITO substrate yields the best performance of PLECs, due to the improvement of interface formation and electrical contact of the ITO substrate with the polymer blend in the PLECs.

Biomimetic polymeric superhydrophobic surfaces and nanostructures: from fabrication to applications.

PubMed

Wen, Gang; Guo, ZhiGuang; Liu, Weimin

2017-03-09

Numerous research studies have contributed to the development of mature superhydrophobic systems. The fabrication and applications of polymeric superhydrophobic surfaces have been discussed and these have attracted tremendous attention over the past few years due to their excellent properties. In general, roughness and chemical composition, the two most crucial factors with respect to surface wetting, provide the basic criteria for yielding polymeric superhydrophobic materials. Furthermore, with their unique properties and flexible configurations, polymers have been one of the most efficient materials for fabricating superhydrophobic materials. This review aims to summarize the most recent progress in polymeric superhydrophobic surfaces. Significantly, the fundamental theories for designing these materials will be presented, and the original methods will be introduced, followed by a summary of multifunctional superhydrophobic polymers and their applications. The principles of these methods can be divided into two categories: the first involves adding nanoparticles to a low surface energy polymer, and the other involves combining a low surface energy material with a textured surface, followed by chemical modification. Notably, surface-initiated radical polymerization is a versatile method for a variety of vinyl monomers, resulting in controlled molecular weights and low polydispersities. The surfaces produced by these methods not only possess superhydrophobicity but also have many applications, such as self-cleaning, self-healing, anti-icing, anti-bioadhesion, oil-water separation, and even superamphiphobic surfaces. Interestingly, the combination of responsive materials and roughness enhances the responsiveness, which allows the achievement of intelligent transformation between superhydrophobicity and superhydrophilicity. Nevertheless, surfaces with poor physical and chemical properties are generally unable to withstand the severe conditions of the outside world; thus, it is necessary to optimize the performances of such materials to yield durable superhydrophobic surfaces. To sum up, some challenges and perspectives regarding the future research and development of polymeric superhydrophobic surfaces are presented.

Vacuum deposition and curing of liquid monomers apparatus

DOEpatents

Affinito, J.D.

1996-08-20

The present invention is the formation of solid polymer layers under vacuum. More specifically, the present invention is the use of ``standard`` polymer layer-making equipment that is generally used in an atmospheric environment in a vacuum, and degassing the monomer material prior to injection into the vacuum. Additional layers of polymer or metal or oxide may be vacuum deposited onto solid polymer layers. Formation of polymer layers under a vacuum improves material and surface characteristics, and subsequent quality of bonding to additional layers. Further advantages include use of less to no photoinitiator for curing, faster curing, fewer impurities in the polymer electrolyte, as well as improvement in material properties including no trapped gas resulting in greater density, and reduced monomer wetting angle that facilitates spreading of the monomer and provides a smoother finished surface. 3 figs.

Design of Stomach Acid-Stable and Mucin-Binding Enzyme Polymer Conjugates.

PubMed

Cummings, Chad S; Campbell, Alan S; Baker, Stefanie L; Carmali, Sheiliza; Murata, Hironobu; Russell, Alan J

2017-02-13

The reduced immunogenicity and increased stability of protein-polymer conjugates has made their use in therapeutic applications particularly attractive. However, the physicochemical interactions between polymer and protein, as well as the effect of this interaction on protein activity and stability, are still not fully understood. In this work, polymer-based protein engineering was used to examine the role of polymer physicochemical properties on the activity and stability of the chymotrypsin-polymer conjugates and their degree of binding to intestinal mucin. Four different chymotrypsin-polymer conjugates, each with the same polymer density, were synthesized using "grafting-from" atom transfer radical polymerization. The influence of polymer charge on chymotrypsin-polymer conjugate mucin binding, bioactivity, and stability in stomach acid was determined. Cationic polymers covalently attached to chymotrypsin showed high mucin binding, while zwitterionic, uncharged, and anionic polymers showed no mucin binding. Cationic polymers also increased chymotrypsin activity from pH 6-8, while zwitterionic polymers had no effect, and uncharged and anionic polymers decreased enzyme activity. Lastly, cationic polymers decreased the tendency of chymotrypsin to structurally unfold at extremely low pH, while uncharged and anionic polymers induced unfolding more quickly. We hypothesized that when polymers are covalently attached to the surface of a protein, the degree to which those polymers interact with the protein surface is the predominant determinant of whether the polymer will stabilize or inactivate the protein. Preferential interactions between the polymer and the protein lead to removal of water from the surface of the protein, and this, we believe, inactivates the enzyme.

Surface modification of SU8 photoresist for shrinkage improvement in a monolithic MEMS microstructure

NASA Astrophysics Data System (ADS)

Chung, C. K.; Hong, Y. Z.

2007-02-01

The effect of O2 plasma treatment on the surface property of exposed and unexposed SU8 photoresist has been investigated for the fabrication of a monolithic MEMS microstructure. It can solve the non-uniformity problem of second resist coating on the SU8 with high intrinsic shrinkage after exposure and post-exposure baking (PEB) in the fabrication of the stacked polymer-metal or polymer-polymer structure, which was used in the application of microfluid, bio and chemistry. The thickness difference of untreated SU8 before PEB between the exposed and unexposed SU8 was about 0.3% while that after PEB increased to about 6%. It could result in large non-uniformity of about 18 µm thickness difference for the following second resist coating on the hydrophobic surface without plasma treatment. The surface property of SU8 in terms of the contact angle and surface energy can be adjusted by O2 plasma treatment for enhancing the coating uniformity of the following resist. The measured contact angles of the exposed and unexposed SU8 decrease with O2 plasma time, corresponding to the increased surface energy determined by the Lifshitz-van der Waals/Lewis acid-base approach. It displayed that the similar hydrophilic surface property can minimize the thickness difference of second resist coating on the first shrunken SU8. A monolithic nozzle plate with a physical resolution of 600 dpi in a single column was demonstrated for an inkjet application based on the improved uniformity.

Path-Integration Computation of the Transport Properties of Polymers Nanoparticles and Complex Biological Structures

NASA Astrophysics Data System (ADS)

Douglas, Jack

2014-03-01

One of the things that puzzled me when I was a PhD student working under Karl Freed was the curious unity between the theoretical descriptions of excluded volume interactions in polymers, the hydrodynamic properties of polymers in solution, and the critical properties of fluid mixtures, gases and diverse other materials (magnets, superfluids,etc.) when these problems were formally expressed in terms of Wiener path integration and the interactions treated through a combination of epsilon expansion and renormalization group (RG) theory. It seemed that only the interaction labels changed from one problem to the other. What do these problems have in common? Essential clues to these interrelations became apparent when Karl Freed, myself and Shi-Qing Wang together began to study polymers interacting with hyper-surfaces of continuously variable dimension where the Feynman perturbation expansions could be performed through infinite order so that we could really understand what the RG theory was doing. It is evidently simply a particular method for resuming perturbation theory, and former ambiguities no longer existed. An integral equation extension of this type of exact calculation to ``surfaces'' of arbitrary fixed shape finally revealed the central mathematical object that links these diverse physical models- the capacity of polymer chains, whose value vanishes at the critical dimension of 4 and whose magnitude is linked to the friction coefficient of polymer chains, the virial coefficient of polymers and the 4-point function of the phi-4 field theory,...Once this central object was recognized, it then became possible solve diverse problems in material science through the calculation of capacity, and related ``virials'' properties, through Monte Carlo sampling of random walk paths. The essential ideas of this computational method are discussed and some applications given to non-trivial problems: nanotubes treated as either rigid rods or ensembles worm-like chains having finite cross-section, DNA, nanoparticles with grafted chain layers and knotted polymers. The path-integration method, which grew up from research in Karl Freed's group, is evidently a powerful tool for computing basic transport properties of complex-shaped objects and should find increasing application in polymer science, nanotechnological applications and biology.

Investigating buried polymer interfaces using sum frequency generation vibrational spectroscopy

PubMed Central

Chen, Zhan

2010-01-01

This paper reviews recent progress in the studies of buried polymer interfaces using sum frequency generation (SFG) vibrational spectroscopy. Both buried solid/liquid and solid/solid interfaces involving polymeric materials are discussed. SFG studies of polymer/water interfaces show that different polymers exhibit varied surface restructuring behavior in water, indicating the importance of probing polymer/water interfaces in situ. SFG has also been applied to the investigation of interfaces between polymers and other liquids. It has been found that molecular interactions at such polymer/liquid interfaces dictate interfacial polymer structures. The molecular structures of silane molecules, which are widely used as adhesion promoters, have been investigated using SFG at buried polymer/silane and polymer/polymer interfaces, providing molecular-level understanding of polymer adhesion promotion. The molecular structures of polymer/solid interfaces have been examined using SFG with several different experimental geometries. These results have provided molecular-level information about polymer friction, adhesion, interfacial chemical reactions, interfacial electronic properties, and the structure of layer-by-layer deposited polymers. Such research has demonstrated that SFG is a powerful tool to probe buried interfaces involving polymeric materials, which are difficult to study by conventional surface sensitive analytical techniques. PMID:21113334

Effect of end segment on physicochemical properties and platelet compatibility of poly(propylene glycol)-initiated poly(methyl methacrylate).

PubMed

Fukuda, Chihiro; Yahata, Chie; Kinoshita, Takuya; Watanabe, Takafumi; Tsukamoto, Hideo; Mochizuki, Akira

2017-10-01

It is well known that polyether-based copolymers have good blood compatibility, although many mechanisms have been proposed to explain their favorable performance. Our objective in carrying out the present study was to obtain a better understanding of the effect of the (poly)ether segment on blood compatibility. Therefore, we synthesized poly(propylene glycol) (PPG)-based initiators for atom transfer polymerization, where the number of propylene glycol (PG) units in the PPG (Pn(PG) was varied from 1 to 94. Methyl methacrylate (MMA) was polymerized using the initiators, resulting in the formation of polyMMAs with a PG-based ether part at the polymer terminal. We mainly investigated the effects of Pn(PG) on the surface properties and platelet compatibility of the PPG-polyMMA. X-ray photoelectron spectroscopy and surface contact angle (CA) analysis revealed the exposure of the PG units at the surface of the polymer. The platelet compatibility of the polymers was improved compared with a commercial polyMMA, even when Pn(PG) = 1. These results suggest that PG units have an important influence on favorable blood compatibility, regardless of the Pn(PG) value. We also investigated protein adsorption behavior in terms of the amount and deformation of fibrinogen adsorbed on the polymer surface.

Enhanced mechanical properties of low-surface energy thin films by simultaneous plasma polymerization of fluorine and epoxy containing polymers

NASA Astrophysics Data System (ADS)

Karaman, Mustafa; Uçar, Tuba

2016-01-01

Thin films of poly(2,2,3,4,4,4 hexafluorobutyl acrylate-glycidyl methacrylate) (P(HFBA-GMA) were deposited on different surfaces using an inductively coupled RF plasma reactor. Fluorinated polymer was used to impart hydrophobicity, whereas epoxy polymer was used for improved durability. The deposition at a low plasma power and temperature was suitable for the functionalization of fragile surfaces such as textile fabrics. The coated rough textile surfaces were found to be superhydrophobic with water contact angles greater than 150° due to the high retention of long fluorinated side chains. The hydrophobicity of the surfaces was observed to be stable after many exposures to ultrasonification tests, which is attributed to the mechanical durability of the films due to their epoxide functionality. FTIR and XPS analyses of the deposited films confirmed that the epoxide functionality of the polymers increased with increasing glycidyl methacrylate fraction in the reactor inlet. The modulus and hardness values of the films also increase with increasing epoxide functionality.

Surface functionalization of metal organic frameworks for mixed matrix membranes

DOEpatents

Albenze, Erik; Lartey, Michael; Li, Tao; Luebke, David R.; Nulwala, Hunaid B.; Rosi, Nathaniel L.; Venna, Surendar R.

2017-03-21

Mixed Matrix Membrane (MMM) are composite membranes for gas separation and comprising a quantity of inorganic filler particles, in particular metal organic framework (MOF), dispersed throughout a polymer matrix comprising one or more polymers. This disclosure is directed to MOF functionalized through addition of a pendant functional group to the MOF, in order to improve interaction with a surrounding polymer matrix in a MMM. The improved interaction aids in avoiding defects in the MMM due to incompatible interfaces between the polymer matrix and the MOF particle, in turn increasing the mechanical and gas separation properties of the MMM. The disclosure is also directed to a MMM incorporating the surface functionalized MOF.

Controlling surface-segregation of a polymer to display carboxy groups on an outermost surface using perfluoroacyl groups.

PubMed

Nishimori, Keisuke; Kitahata, Shigeru; Nishino, Takashi; Maruyama, Tatsuo

2018-05-10

Controlling the surface properties of solid polymers is important for practical applications. We here succeeded in controlling the surface segregation of polymers to display carboxy groups on an outermost surface, which allowed the covalent immobilization of functional molecules via the carboxy groups on a substrate surface. Random methacrylate-based copolymers containing carboxy groups, in which carboxy groups were protected with perfluoroacyl (Rf) groups, were dip-coated on acrylic substrate surfaces. X-ray photoelectron spectroscopy and contact-angle measurements revealed that the Rf groups were segregated to the outermost surface of the dip-coated substrates. The Rf groups were removed by hydrolysis of the Rf esters in the copolymers, resulting in the display of carboxy groups on the surface. The quantification of carboxy groups on a surface revealed that the carboxy groups were reactive to a water-soluble solute in aqueous solution. The surface segregation was affected by the molecular structure of the copolymer used for dip-coating.

Preparation of immobilized glucose oxidase wafer enzyme on calcium-bentonite modified by surfactant

NASA Astrophysics Data System (ADS)

Widi, R. K.; Trisulo, D. C.; Budhyantoro, A.; Chrisnasari, R.

2017-07-01

Wafer glucose oxidase (GOx) enzymes was produced by addition of PAH (Poly-Allyamine Hydrochloride) polymer into immobilized GOx enzyme on modified-Tetramethylammonium Hydroxide (TMAH) 5%-calsium-bentonite. The use of surfactant molecul (TMAH) is to modify the surface properties and pore size distribution of the Ca-bentonite. These properties are very important to ensure GOx molecules can be bound on the Ca-bentonit surface to be immobilized. The addition of the polymer (PAH) is expected to lead the substrates to be adsorbed onto the enzyme. In this study, wafer enzymes were made in various concentration ratio (Ca-bentonite : PAH) which are 1:0, 1:1, 1:2 and 1:3. The effect of PAH (Poly-Allyamine Hydrochloride) polymer added with various ratios of concentrations can be shown from the capacitance value on LCR meter and enzyme activity using DNS method. The addition of the polymer (PAH) showed effect on the activity of GOx, it can be shown from the decreasing of capacitance value by increasing of PAH concentration.

Computer-aided design of polymers and composites

NASA Technical Reports Server (NTRS)

Kaelble, D. H.

1985-01-01

This book on computer-aided design of polymers and composites introduces and discusses the subject from the viewpoint of atomic and molecular models. Thus, the origins of stiffness, strength, extensibility, and fracture toughness in composite materials can be analyzed directly in terms of chemical composition and molecular structure. Aspects of polymer composite reliability are considered along with characterization techniques for composite reliability, relations between atomic and molecular properties, computer aided design and manufacture, polymer CAD/CAM models, and composite CAD/CAM models. Attention is given to multiphase structural adhesives, fibrous composite reliability, metal joint reliability, polymer physical states and transitions, chemical quality assurance, processability testing, cure monitoring and management, nondestructive evaluation (NDE), surface NDE, elementary properties, ionic-covalent bonding, molecular analysis, acid-base interactions, the manufacturing science, and peel mechanics.

Structural and Interfacial Properties of Hyperbranched-Linear Polymer Surfactant.

PubMed

Qiang, Taotao; Bu, Qiaoqiao; Huang, Zhaofeng; Wang, Xuechuan

2014-01-01

With oleic acid grafting modification, a series of hyperbranched-linear polymer surfactants (HLPS) were prepared by hydroxyl-terminated hyperbranched polymer (HBP), which was gained through a step synthesis method using trimethylolpropane and AB 2 monomer. The AB 2 monomers were obtained through the Michael addition reaction of methyl acrylate and diethanol amine. The structures of HLPS were characterised by Fourier transform infrared spectrophotometer and nuclear magnetic resonance (NMR), which indicated that HBP was successfully modified by oleic acid. Furthermore, the properties of surface tension and critical micelle concentration of HLPS solution showed that HLPS can significantly reduce the surface tension of water. The morphology of the HLPS solution was characterised by dynamic light scattering, which revealed that HLPS exhibited a nonmonotonic appearance in particle size at different scattering angles owing to the different replaced linear portions. The relationships of the surface pressure to monolayer area and time were measured using the Langmuir-Blodgett instrument, which showed that the surface tension of monolayer molecules increased with the increasing of hydrophobic groups. In addition, the interface conditions of different replaced HLPS solutions were simulated.

The deposition of thin titanium-nitrogen coatings on the surface of PCL-based scaffolds for vascular tissue engineering

NASA Astrophysics Data System (ADS)

Kudryavtseva, Valeriya; Stankevich, Ksenia; Kibler, Elina; Golovkin, Alexey; Mishanin, Alexander; Bolbasov, Evgeny; Choynzonov, Evgeny; Tverdokhlebov, Sergei

2018-04-01

Biodegradable polymer scaffolds for tissue engineering is a promising technology for therapies of patients suffering from the loss of tissue or its function including cardiac tissues. However, limitations such as hydrophobicity of polymers prevent cell attachment, cell conductivity, and endothelialization. Plasma modification of polymers allows producing materials for an impressive range of applications due to their unique properties. Here, we demonstrate the possibility of bioresorbable electrospun polycaprolacton (PCL) scaffold surface modification by reactive magnetron sputtering of the titanium target in a nitrogen atmosphere. The influence of the plasma treatment time on the structure and properties of electrospun PCL scaffolds was studied. We show that the plasma treatment does not change the physico-mechanical properties of electrospun PCL scaffolds, leads to an increase in PCL scaffold biocompatibility, and, simultaneously, increases their hydrophilicity. In conclusion, this modification method opens a route to producing scaffolds with enhanced biocompatibility for tissue engineered vascular grafts.

Interfacial friction and adhesion of cross-linked polymer thin films swollen with linear chains.

PubMed

Zhang, Qing; Archer, Lynden A

2007-07-03

The preparation and interfacial properties of a new type of tethered, thin-film lubricant coating are presented. These coatings are composed of three components: a dense self-assembled monolayer (SAM) underlayer that presents reactive vinyl groups at its surface; a cross-linked polydimethylsiloxane (PDMS) overlayer that is covalently tethered to the SAM; and free, mobile linear PDMS chains dispersed in the network. We investigate the influence of the molecular weight (Ms) and concentration of the free PDMS chains on the structure and equilibrium swelling properties of the cross-linked films. Using a bead-probe lateral force microscopy measurement technique, we also quantify the interfacial friction and adhesion characteristics of surfaces functionalized with these coatings. We find that both the volume fraction and the molecular weight of free PDMS molecules in the coatings influence their interfacial friction and adhesion properties. For example, the addition of short PDMS chains in dry, cross-linked PDMS thin films yields tethered surface coatings with ultralow friction coefficients (mu = 5.2 x 10(-3)). An analysis based on classical lubrication theory suggests that the reduction in friction force produced by free polymer is a consequence of the gradual separation of asperities on opposing surfaces and the consequent substitution of solid-solid friction by viscous drag of the free polymer chains in the network.

DNA immobilization and detection on cellulose paper using a surface grown cationic polymer via ATRP.

PubMed

Aied, Ahmed; Zheng, Yu; Pandit, Abhay; Wang, Wenxin

2012-02-01

Cationic polymers with various structures have been widely investigated in the areas of medical diagnostics and molecular biology because of their unique binding properties and capability to interact with biological molecules in complex biological environments. In this work, we report the grafting of a linear cationic polymer from an atom transfer radical polymerization (ATRP) initiator bound to cellulose paper surface. We show successful binding of ATRP initiator onto cellulose paper and grafting of polymer chains from the immobilized initiator with ATRP. The cellulose paper grafted polymer was used in combination with PicoGreen (PG) to demonstrate detection of nucleic acids in the nanogram range in homogeneous solution and in a biological sample (serum). The results showed specific identification of hybridized DNA after addition of PG in both solutions.

Flexible Substrates Comparison for Pled Technology

NASA Astrophysics Data System (ADS)

Nenna, G.; Miscioscia, R.; Tassini, P.; Minarini, C.; Vacca, P.; Valentino, O.

2008-08-01

Flexible substrate displays are critical to organic electronics, e-paper's and e-ink's development. Many different types of materials are under investigation, including glass, polymer films and metallic foils. In this work we report a comparison study of polymer films as flexible substrates for polymer light emitting diodes (PLEDs) technology. The selected polymer substrates are two thermoplastic semi-crystalline polymers (PET and PEN) and a high Tg material that cannot be melt processed (PAR). Firstly, the chosen films were characterized in morphology and optical properties with the aim to confirm their suitability for optoelectronic applications. Transmittance was analysed by UV-Vis spectrophotometry and roughness by a surface profilometer. Finally, the surface energy of substrates (untreated and after UV-ozone treatment) was estimated by contact angle measurements in order to evaluate their wettability for active materials deposition.

Clear, Conductive, Transparent, Flexible Space Durable Composite Films for Electrostatic Charge Mitigation

NASA Technical Reports Server (NTRS)

Watson, Kent A.; Connell, John W.; Delozier, Donavon M.; Smith, Joseph G., Jr.

2004-01-01

Space environmentally durable polymeric films with low color and sufficient electrical conductivity to mitigate electrostatic charge (ESC) build-up have been under investigation as part of a materials development activity. These materials have potential applications on advanced spacecraft, particularly on large, deployable, ultra-light weight Gossamer spacecraft. The approach taken to impart sufficient electrical conductivity into the polymer film while maintaining flexibility is to use single wall carbon nanotubes (SWNTs) as conductive additives. Approaches investigated in our lab involved an in-situ polymerization method, addition of SWNTs to a polymer containing reactive end-groups, and spray coating of polymer surfaces. The work described herein is a summary of the current status of this project. Surface conductivities (measured as surface resistance) in the range sufficient for ESC mitigation were achieved with minimal effects on the physical, thermal, mechanical and optical properties of the films. Additionally, the electrical conductivity was not affected by harsh mechanical manipulation of the films. The chemistry and physical properties of these nanocomposites will be discussed.

Surface changes of biopolymers PHB and PLLA induced by Ar+ plasma treatment and wet etching

NASA Astrophysics Data System (ADS)

Slepičková Kasálková, N.; Slepička, P.; Sajdl, P.; Švorčík, V.

2014-08-01

Polymers, especially group of biopolymers find potential application in a wide range of disciplines due to their biodegradability. In biomedical applications these materials can be used as a scaffold or matrix. In this work, the influence of the Ar+ plasma treatment and subsequent wet etching (acetone/water) on the surface properties of polymers were studied. Two biopolymers - polyhydroxybutyrate with 8% polyhydroxyvalerate (PHB) and poly-L-lactic acid (PLLA) were used in these experiments. Modified surface layers were analyzed by different methods. Surface wettability was characterized by determination of water contact angle. Changes in elemental composition of modified surfaces were performed by X-ray Photoelectron Spectroscopy (XPS). Surface morphology and roughness was examined using Atomic Force Microscopy (AFM). Gravimetry method was used to study the mass loss. It was found that the modification from both with plasma and wet etching leads to dramatic changes of surface properties (surface chemistry, morphology and roughness). Rate of changes of these features strongly depends on the modification parameters.

Functionalization of polymer powders for SLS-processes using an atmospheric plasma jet in a fluidized bed reactor

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

Sachs, Marius; Schmitt, Adeliene; Schmidt, Jochen

2015-05-22

Recently additive manufacturing processes such as selective laser sintering (SLS) of polymers have gained more importance for industrial applications [1]. Tailor-made modification of polymers is essential in order to make these processes more efficient and to cover the industrial demands. The so far used polymer materials show weak performance regarding the mechanical stability of processed parts. To overcome this limitation, a new route to functionalize the surface of commercially available polymer particles (PA12; PE-HD; PP) using an atmospheric plasma jet in combination with a fluidized bed reactor has been investigated. Consequently, an improvement of adhesion and wettability [2] of themore » polymer surface without restraining the bulk properties of the powder is achieved. The atmospheric plasma jet process can provide reactive species at moderate temperatures which are suitable for polymer material. The functionalization of the polymer powders improves the quality of the devices build in a SLS-process.« less

Optical, thermal and morphological study of ZnS doped PVA polymer nano composites

NASA Astrophysics Data System (ADS)

Guruswamy, B.; Ravindrachary, V.; Shruthi, C.; Sagar, Rohan N.; Hegde, Shreedatta

2018-05-01

The effect of ZnS nano particle doping on optical, thermal properties and morphological study of the PVA polymer has been investigated using FTIR, UV-Visible and TGA, FESEM techniques. Nano sized ZnS particles were synthesized by a simple wet chemical route. Pure and ZnS/PVA nano composites were prepared using solution casting technique. The FTIR study confirms that the ZnS nano particles interacts with the OH group of PVA polymer and forms the complex. The formation of these complexes affects the optical and thermal properties of the composite. The changes in optical properties were studied using UV-Vis absorption method. The variation in thermal property was analysed using TGA results. The modified surface morphology analysis was carried out using FESEM.

Advances in mucoadhesion and mucoadhesive polymers.

PubMed

Khutoryanskiy, Vitaliy V

2011-06-14

Mucoadhesion is the ability of materials to adhere to mucosal membranes in the human body and provide a temporary retention. This property has been widely used to develop polymeric dosage forms for buccal, oral, nasal, ocular and vaginal drug delivery. Excellent mucoadhesive properties are typical for hydrophilic polymers possessing charged groups and/or non-ionic functional groups capable of forming hydrogen bonds with mucosal surfaces. This feature article considers recent advances in the study of mucoadhesion and mucoadhesive polymers. It provides an overview on the structure of mucosal membranes, properties of mucus gels and the nature of mucoadhesion. It describes the most common methods to evaluate mucoadhesive properties of various dosage forms and discusses the main classes of mucoadhesives. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymer-ceramic nanocomposites for applications in the bone surgery

NASA Astrophysics Data System (ADS)

Stodolak, E.; Gadomska, K.; Lacz, A.; Bogun, M.

2009-01-01

The subject of this work was preparation and investigation of properties of a nanocomposite material based on polymer matrix modified with nanometric silica particles (SiO2). The composite matrix consisted of resorbable P(L/DL)LA polymer with certified biocompatibility. Nanometric silica was introduced into the matrix by means of ultrasonic homogenisation and/or mechanical stirring. The silica was introduced directly e.g. as nanoparticles or inside calcium alginate fibres which contained 3 wt.% of amorphous SiO2. Proper dispersion of nano-filliers was confirmed by means of thermal analysis (TG/DTA, DSC). It was observed, that the presence of inorganic nanoparticles influenced several surface parameters of the nanocomposites i.e. hydrophility (a decrease of surface energy) and topography (both in micro- and nano-scale). Additionally, the nanocomposites exhibited enhanced mechanical properties (Young's modulus, tensile strength) compared to the pure polymer. The nanocomposites were bioactive materials (SBF/3 days/37oC). Biological tests (MTT test) showed a good viability of human osteoblasts (hFOB 1.19) in contact with the nanocomposites surface. Results of preliminary biological tests carried out with the use of mother cells extracted from human bone marrow showed that the nanocomposites may provide differenation of bone cells.

Tuning the structure of thermosensitive gold nanoparticle monolayers.

PubMed

Rezende, Camila A; Shan, Jun; Lee, Lay-Theng; Zalczer, Gilbert; Tenhu, Heikki

2009-07-23

Gold nanoparticles grafted with poly(N-isopropylacrylamide) (PNIPAM) are rendered amphiphilic and thermosensitive. When spread on the surface of water, they form stable Langmuir monolayers that exhibit surface plasmon resonance. Using Langmuir balance and contrast-matched neutron reflectivity, the detailed structural properties of these nanocomposite monolayers are revealed. At low surface coverage, the gold nanoparticles are anchored to the interface by an adsorbed PNIPAM layer that forms a thin and compact pancake structure. Upon isothermal compression (T=20 degrees C), the adsorbed layer thickens with partial desorption of polymer chains to form brush structures. Two distinct polymer conformations thus coexist: an adsorbed conformation that assures stability of the monolayer, and brush structures that dangle in the subphase. An increase in temperature to 30 degrees C results in contractions of both adsorbed and brush layers with a concomitant decrease in interparticle distance, indicating vertical as well as lateral contractions of the graft polymer layer. The reversibility of this thermal response is also shown by the contraction-expansion of the polymer layers in heating-cooling cycles. The structure of the monolayer can thus be tuned by compression and reversibly by temperature. These compression and thermally induced conformational changes are discussed in relation to optical properties.

Processing and properties of ceramic matrix-polymer composites for dental applications

NASA Astrophysics Data System (ADS)

Huang, Hsuan Yao

The basic composite structure of natural hard tissue was used to guide the design and processing of dental restorative materials. The design incorporates the methodology of using inorganic minerals as the main structural phase reinforced with a more ductile but tougher organic phase. Ceramic-polymer composites were prepared by slip casting a porous ceramic structure, heating and chemical treating the porous preform, infiltrating with monomer and then curing. The three factors that determined the mechanical properties of alumina-polymer composites were the type of polymer used, the method of silane treatments, and the type of bond between particles in the porous preforms. Without the use of silane coupling agents, the composites were measured to have a lower strength. The composite with a more "flexible" porous alumina network had a greater ability to plastically dissipate the energy of propagating cracks. However, the aggressive nature of the alumina particles on opposing enamel requires that these alumina-polymer composites have a wear compatible coating for practical application. A route to dense bioactive apatite wollastonite glass ceramics (AWGC)-polymer composites was developed. The problems associated with glass dissolution into the aqueous medium for slip casting were overcome with the use of silane. The role of heating rate and development of ceramic compact microstructure on composite properties was explored. In general, if isothermal heating was not applied, decreasing heating rate increased glass crystallinity and particle-particle fusion, but decreased pore volume. Also composite strength and fracture toughness decreased while modulus and hardness increased with decreasing heating rate. If isothermal heating was applied, glass crystallinity, pore content, and composite mechanical properties showed relatively little change regardless of the initial heating rate. The potential of AWGC-polymer composites for dental and implant applications was explored. Strengths and toughnesses were not severely degraded by immersion in simulated body fluids up to 30 days. The composite elastic modulus approached that of hard tissues and its wear behavior with opposing tooth was excellent. Growth of apatite over the entire composite surface was achieved in SBF. Growth of apatite in human whole saliva was achieved on the bioactive glass surface, but not on the composite surface.

Nanopatterned polymer brushes: conformation, fabrication and applications.

PubMed

Yu, Qian; Ista, Linnea K; Gu, Renpeng; Zauscher, Stefan; López, Gabriel P

2016-01-14

Surfaces with end-grafted, nanopatterned polymer brushes that exhibit well-defined feature dimensions and controlled chemical and physical properties provide versatile platforms not only for investigation of nanoscale phenomena at biointerfaces, but also for the development of advanced devices relevant to biotechnology and electronics applications. In this review, we first give a brief introduction of scaling behavior of nanopatterned polymer brushes and then summarize recent progress in fabrication and application of nanopatterned polymer brushes. Specifically, we highlight applications of nanopatterned stimuli-responsive polymer brushes in the areas of biomedicine and biotechnology.

Nanopatterned polymer brushes: conformation, fabrication and applications

NASA Astrophysics Data System (ADS)

Yu, Qian; Ista, Linnea K.; Gu, Renpeng; Zauscher, Stefan; López, Gabriel P.

2015-12-01

Surfaces with end-grafted, nanopatterned polymer brushes that exhibit well-defined feature dimensions and controlled chemical and physical properties provide versatile platforms not only for investigation of nanoscale phenomena at biointerfaces, but also for the development of advanced devices relevant to biotechnology and electronics applications. In this review, we first give a brief introduction of scaling behavior of nanopatterned polymer brushes and then summarize recent progress in fabrication and application of nanopatterned polymer brushes. Specifically, we highlight applications of nanopatterned stimuli-responsive polymer brushes in the areas of biomedicine and biotechnology.

Computational design of surfaces, nanostructures and optoelectronic materials

NASA Astrophysics Data System (ADS)

Choudhary, Kamal

Properties of engineering materials are generally influenced by defects such as point defects (vacancies, interstitials, substitutional defects), line defects (dislocations), planar defects (grain boundaries, free surfaces/nanostructures, interfaces, stacking faults) and volume defects (voids). Classical physics based molecular dynamics and quantum physics based density functional theory can be useful in designing materials with controlled defect properties. In this thesis, empirical potential based molecular dynamics was used to study the surface modification of polymers due to energetic polyatomic ion, thermodynamics and mechanics of metal-ceramic interfaces and nanostructures, while density functional theory was used to screen substituents in optoelectronic materials. Firstly, polyatomic ion-beams were deposited on polymer surfaces and the resulting chemical modifications of the surface were examined. In particular, S, SC and SH were deposited on amorphous polystyrene (PS), and C2H, CH3, and C3H5 were deposited on amorphous poly (methyl methacrylate) (PMMA) using molecular dynamics simulations with classical reactive empirical many-body (REBO) potentials. The objective of this work was to elucidate the mechanisms by which the polymer surface modification took place. The results of the work could be used in tailoring the incident energy and/or constituents of ion beam for obtaining a particular chemistry inside the polymer surface. Secondly, a new Al-O-N empirical potential was developed within the charge optimized many body (COMB) formalism. This potential was then used to examine the thermodynamic stability of interfaces and mechanical properties of nanostructures composed of aluminum, its oxide and its nitride. The potentials were tested for these materials based on surface energies, defect energies, bulk phase stability, the mechanical properties of the most stable bulk phase, its phonon properties as well as with a genetic algorithm based evolution theory of the materials to ensure that no spurious phases had a lower cohesive energy. Thirdly, lanthanide doped and co-doped Y3Al5O 12 were examined using density functional theory (DFT) with semi-local and local functional. Theoretical results were compared and validated with experimental data and new co-doped materials with high efficiency were predicted. Finally, Transition element doped CH3NH3PbI3 were studied with DFT for validation of the model with experimental data and replacement materials for toxic Pb were predicted.

Thermomechanical properties of polymer nanocomposites: Exploring a unified relationship with planar polymer films

NASA Astrophysics Data System (ADS)

Bansal, Amitabh

The thermal and mechanical response of polymers, which provide limitations to their practical use, are greatly improved by the addition of a small fraction of an inorganic nanofiller. However, the resulting changes in polymer properties are poorly understood, primarily due to the non-uniform spatial distribution of nanoparticles. This research explores the properties of polystyrene filed with silica nanoparticles and illustrates for the first time that the thermodynamic properties of "polymer nanocomposites" are quantitatively equivalent to the well-understood case of planar polymer films with a uniform thickness. These ideas are quantified by drawing a direct analogy between thin film thickness and an appropriate average ligament thickness measured using electron microscopy. The change in polymer glass transition temperatures with decreasing ligament thickness were found to be quantitatively equivalent to the corresponding thin film data. In combination with viscoelastic properties of the nanocomposites that are in quantitative agreement with data from thin films, these conclusions provide a facile means of understanding and predicting the thermomechanical properties and, potentially, the engineering properties of practically relevant polymer nanocomposites. Grafting of high molecular weight polystyrene onto the silica nanoparticles greatly improves the dispersion quality of nanofillers and also provides a means to tailor the thermo-mechanical properties in nanocomposites. It is concluded that the grafted polystyrene is akin to polymer brushes on flat surfaces. The mobility and stiffness of these grafted chains are expected to be low as compared to the free polymer. In this context a mechanism for the increase in glass transition is proposed: (1) the stiff grafted chains will tend to decrease mobility and thus increase glass transition, (2) the extent of interdigitation of the grafted polystyrene into the matrix will determine the extent to which the nanocomposite properties are effected, and (3) these effects leading to slower dynamics compete with confinement effects due to the proximity of silica nanoparticles. It is shown that the well understood behavior of polymers next to flat interfaces can be used effectively to predict nanocomposite behavior. More exploration in this direction will lead to considerable scientific and technological development.

Nano-Sized Cyclodextrin-Based Molecularly Imprinted Polymer Adsorbents for Perfluorinated Compounds—A Mini-Review

PubMed Central

Karoyo, Abdalla H.; Wilson, Lee D.

2015-01-01

Recent efforts have been directed towards the design of efficient and contaminant selective remediation technology for the removal of perfluorinated compounds (PFCs) from soils, sediments, and aquatic environments. While there is a general consensus on adsorption-based processes as the most suitable methodology for the removal of PFCs from aquatic environments, challenges exist regarding the optimal materials design of sorbents for selective uptake of PFCs. This article reviews the sorptive uptake of PFCs using cyclodextrin (CD)-based polymer adsorbents with nano- to micron-sized structural attributes. The relationship between synthesis of adsorbent materials and their structure relate to the overall sorption properties. Hence, the adsorptive uptake properties of CD-based molecularly imprinted polymers (CD-MIPs) are reviewed and compared with conventional MIPs. Further comparison is made with non-imprinted polymers (NIPs) that are based on cross-linking of pre-polymer units such as chitosan with epichlorohydrin in the absence of a molecular template. In general, MIPs offer the advantage of selectivity, chemical tunability, high stability and mechanical strength, ease of regeneration, and overall lower cost compared to NIPs. In particular, CD-MIPs offer the added advantage of possessing multiple binding sites with unique physicochemical properties such as tunable surface properties and morphology that may vary considerably. This mini-review provides a rationale for the design of unique polymer adsorbent materials that employ an intrinsic porogen via incorporation of a macrocyclic compound in the polymer framework to afford adsorbent materials with tunable physicochemical properties and unique nanostructure properties. PMID:28347047

Initial biocompatibility of plasma polymerized hexamethyldisiloxane films with different wettability

NASA Astrophysics Data System (ADS)

Krasteva, N. A.; Toromanov, G.; Hristova, K. T.; Radeva, E. I.; Pecheva, E. V.; Dimitrova, R. P.; Altankov, G. P.; Pramatarova, L. D.

2010-11-01

Understanding the relationships between material surface properties, behaviour of adsorbed proteins and cellular responses is essential to design optimal material surfaces for tissue engineering. In this study we modify thin layers of plasma polymerized hexamethyldisiloxane (PPHMDS) by ammonia treatment in order to increase surface wettability and the corresponding biological response. The physico-chemical properties of the polymer films were characterized by contact angle (CA) measurements and Fourier Transform Infrared Spectroscopy (FTIR) analysis.Human umbilical vein endothelial cells (HUVEC) were used as model system for the initial biocompatibility studies following their behavior upon preadsorption of polymer films with three adhesive proteins: fibronectin (FN), fibrinogen (FG) and vitronectin (VN). Adhesive interaction of HUVEC was evaluated after 2 hours by analyzing the overall cell morphology, and the organization of focal adhesion contacts and actin cytoskeleton. We have found similar good cellular response on FN and FG coated polymer films, with better pronounced vinculin expression on FN samples while. Conversely, on VN coated surfaces the wettability influenced significantly initial celular interaction spreading. The results obtained suggested that ammonia plasma treatment can modulate the biological activity of the adsorbed protein s on PPHMDS surfaces and thus to influence the interaction with endothelial cells.

Replication of Leaf Surface Structures for Light Harvesting

PubMed Central

Huang, Zhongjia; Yang, Sai; Zhang, Hui; Zhang, Meng; Cao, Wei

2015-01-01

As one of the most important hosts of natural light harvesting, foliage normally has complicated surface structures to capture solar radiances. Bio-mimicking leaf surface structures can provide novel designs of covers in photovoltaic systems. In this article, we reported on replicating leaf surface structures on poly-(methyl methacrylate) polymers to prompt harvesting efficiencies. Prepared via a double transfer process, the polymers were found to have high optical transparencies and transmission hazes, with both values exceeding 80% in some species. Benefiting from optical properties and wrinkled surfaces, the biomimetic polymers brought up to 17% gains to photovoltaic efficiencies. Through Monte-Carlo simulations of light transport, ultrahigh haze values and low reflections were attributed to lightwave guidance schemes lead by the nano- and micro-morphologies which are inherited from master leaves. Thus, leaf surface bio-mimicking can be considered as a strategic direction to design covers of light harvesting systems. PMID:26381702

Dynamic Demos.

ERIC Educational Resources Information Center

Sae, Andy S. W.

1991-01-01

Discusses 27 chemical demonstrations involving inexpensive, readily available materials that illustrate the following concepts: acid/base properties, gas properties, characteristics of carbon dioxide, chemiluminescence, freezing point depression, heat of vaporization; density, polymers, surface tension, polarity/nonpolarity, UV absorption,…

Synthesis and characterization of polymer layers for control of fluid transport

NASA Astrophysics Data System (ADS)

Vatansever, Fehime

The level of wetting of fiber surface with liquids is an important characteristic of fibrous materials. It is related to fiber surface energy and the structure of the material. Surface energy can be changed by surface modification via the grafting methodologies that have been reported for introducing new and stable functionality to fibrous substrates without changing bulk properties. Present work is dedicated to synthesis and characterization of macromolecular layers grafted to fiber surface in order to achieve directional liquid transport for the modified fabric. Modification technique used here is based on formation of stable polymer layer on fabric surface using "grafting to" technique. Specifically, modification of fabric with wettability gradient for facilitated one way-liquid transport, and pointed modification of yarn-based channels on textile microfluidic device for directional liquid transport are reported here. First, fabric was activated with alkali (NaOH) solution. Second, poly (glycidyl methacrylate) (PGMA) was deposited on fabric as an anchoring layer. Finally, polymers of interest were grafted to surface through the epoxy functionality of PGMA. Effect of polymer grafting on the wicking property of the fabric has been evaluated by vertical wicking technique at the each step of surface modification. The results shows that wicking performance of fabric can be altered by grafting of a thin nanoscale polymeric film. For the facilitated liquid transport, the gradient polymer coating was created using "grafting to" technique and its dependence on the grafting temperature. Wettability gradient from hydrophilic to hydrophobic (change in water contact angle from 0 to 140 degrees on fabric) was achieved by grafting of polystyrene (PS) and polyacrylic acid (PAA) sequentially with concentration gradient. This study proposes that fabric with wettability gradient property can be used to transfer sweat from skin and support moisture management when it is used in a laminated garment structure. For cooling performance evaluation, modified fabrics were tested with surface differential scanning calorimeter, and improved cooling effect was found with the fabric that has wettability gradient. Directional liquid transport can be achieved on amphiphilic fabric. To this end, fabric consisting of PET and PP yarn is fabricated. Activation and PGMA deposition yields an array of highly reactive PET channels that are constrained by hydrophobic PP boundaries. Aqueous solutions are transported in the channels by capillary forces where the direction of the liquid transport is defined by pH-response of the grafted polymers. The system of pH-selective channels in the developed textile based microfluidic chip could find analytical applications and can be used for smart cloth.

Influence of additives on melt viscosity, surface tension, and film formation of dry powder coatings.

PubMed

Sauer, Dorothea; McGinity, James W

2009-06-01

Limited information on thermally cured dry-powder coatings used for solid dosage forms has been available in the literature. The aim of this study was to characterize the film formation process of Eudragit L 100-55 dry-powder coatings and to investigate the influence of film additives on melt viscosity and surface tension. The coating process employed no liquids and the plasticizer was combined with the polymer using hot melt extrusion. Thermoanalytical methods including differential scanning calorimetry and thermogravimetric analysis (TGA) were used to investigate the thermal properties of the dry-coating formulations. The rheological behavior of the coating formulations were characterized with the extrusion torque, and the surface energy parameters were determined from contact angle measurements. The influence of the level of triethyl citrate (TEC) as plasticizer and polyethylene glycol (PEG) 3350 in the polymer film on film formation was investigated using a digital force tester. TGA confirmed thermal stability of all coating excipients at the investigated curing conditions. Increasing TEC levels and the addition of PEG 3350 as a low melting excipient in the coating reduced the viscosity of the polymer. Plasticization of the polymer with TEC increased the surface free energy, whereas the admixture of 10% PEG 3350 did not affect the surface free energy of Eudragit L 100-55. The spreading coefficient of the polymers over two sample tablet formulations was reduced with increasing surface free energy. During the curing process, puncture strength, and elongation of powder-cast films increased. The effect of curing time on the mechanical properties was dependent on the plasticizer content. The incorporation of TEC and PEG 3350 into the Eudragit L 100-55 powder coating formulation improved film formation. Mechanical testing of powder-cast films showed an increase of both elongation and puncture strength over the curing process as criterion for polymer particle fusion, where film formation progressed faster at high plasticizer levels.

Mechanical reinforcement and segmental dynamics of polymer nanocomposites

NASA Astrophysics Data System (ADS)

Gong, Shushan

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

Interaction of polyhedral oligomeric silsesquioxanes and dipalmitoylphosphatidylcholine at the air/water interface: Thermodynamic and rheological study.

PubMed

Skrzypiec, M; Georgiev, G As; Rojewska, M; Prochaska, K

2017-10-01

Polyhedral oligomeric silsesquioxanes (POSS) derivatives containing open silsesquioxane cage bear great potential for biomedical applications and therefore their lateral interactions with phospholipids, major biomembranes and drug vehicles constituent, should be studied in detail. That is why the properties of surface films by two POSS-derivatives, POSS-polyethylene glycol (POSS-PEG) and POSS-perfluoroalkyl (POSS-OFP), pure and in presence of 1,2-dipalmitoyl-sn-glycerol-3-phosphocholine (DPPC) were studied using Langmuir surface balance. Side chains of opposite nature (PEG is hydrophilic; OFP is hydrophobic) were selected, so that to evaluate their impact on polymers' surface properties. Two types of measurements were performed: (i) the miscibility of POSS-derivatives with DPPC was evaluated via thermodynamic analysis of the surface pressure (π)-area (A) isotherms and (ii) the dilatational rheology of selected POSS-polymer containing films was studied by the stress relaxation method. Fourier transformation analysis of the relaxation transients allows to access films' dynamic interfacial properties in broad frequency range (10 -5 -1Hz). Film morphology was monitored with Brewster Angle Microscopy. PEG moiety enabled POSS-PEG to stably incorporate in DPPC films, modifying their equilibrium and dynamic properties. In contrast OFP chains excluded from interactions with other molecules and diminished PEG-OFP amphiphilicity. Therefore at high packing densities (π≥25mN/m) PEG-OFP was expelled from the air/water interface in DPPC/PEG-OFP mixtures, and the binary films equilibrium and dynamic surface properties were determined primarily by DPPC. Thus the choice of POSS side chains can play key role in biomedical applications depending on whether strong or weak incorporation of POSS-polymers in lipid environment is aimed for. Copyright © 2017 Elsevier B.V. All rights reserved.

Algal antifouling and fouling-release properties of metal surfaces coated with a polymer inspired by marine mussels.

PubMed

Statz, Andrea; Finlay, John; Dalsin, Jeffrey; Callow, Maureen; Callow, James A; Messersmith, Phillip B

2006-01-01

The marine antifouling and fouling-release performance of titanium surfaces coated with a bio-inspired polymer was investigated. The polymer consisted of methoxy-terminated poly(ethylene glycol) (mPEG) conjugated to the adhesive amino acid l-3,4-dihydroxyphenylalanine (DOPA) and was chosen based on its successful resistance to protein and mammalian cell fouling. Biofouling assays for the settlement and release of the diatom Navicula perminuta and settlement, growth and release of zoospores and sporelings (young plants) of the green alga Ulva linza were carried out. Results were compared to glass, a poly(dimethylsiloxane) elastomer (Silastic T2) and uncoated Ti. The mPEG-DOPA3 modified Ti surfaces exhibited a substantial decrease in attachment of both cells of N. perminuta and zoospores of U. linza as well as the highest detachment of attached cells under flow compared to control surfaces. The superior performance of this polymer over a standard silicone fouling-release coating in diatom assays and approximately equivalent performance in zoospore assays suggests that this bio-inspired polymer may be effective in marine antifouling and fouling-release applications.

Selective cell response on natural polymer bio-interfaces textured by femtosecond laser

NASA Astrophysics Data System (ADS)

Daskalova, A.; Trifonov, A.; Bliznakova, I.; Nathala, C.; Ajami, A.; Husinsky, W.; Declercq, H.; Buchvarov, I.

2018-02-01

This study reports on the evaluation of laser processed natural polymer-chitosan, which is under consideration as a biointerface used for temporary applications as skin and cartilage substitutes. It is employed for tissue engineering purposes, since it possesses a significant degree of biocompatibility and biodegradability. Chitosan-based thin films were processed by femtosecond laser radiation to enhance the surface properties of the material. Various geometry patterns were produced on polymer surfaces and employed to examine cellular adhesion and orientation. The topography of the modified zones was observed using scanning electron microscopy and confocal microscopy. Test of the material cytotoxicity was performed by evaluating the life/dead cell correlation. The obtained results showed that texturing with femtosecond laser pulses is appropriate method to initiate a predefined cellular response. Formation of surface modifications in the form of foams with an expansion of the material was created under laser irradiation with a number of applied laser pulses from N = 1-5. It is shown that irradiation with N > 5 results in disturbance of microfoam. Material characterization reveals a decrease in water contact angle values after laser irradiation of chitosan films. Consequently, changes in surface roughness of chitosan thin-film surface result in its functionalization. Cultivation of MC3T3 and ATMSC cells show cell orientational migration concerning different surface patterning. The influence of various pulse durations (varying from τ = 30-500 fs) over biofilms surface was examined regarding the evolution of surface morphology. The goal of this study was to define the optimal laser conditions (laser energy, number of applied pulses, and pulse duration) to alter surface wettability properties and porosity to improve material performance. The acquired set of results indicate the way to tune the surface properties to optimize cell-interface interaction.

General and Robust Strategies for Multifunctional Organic-Inorganic Nanocompositesvia Direct Growth of Monodisperse Nanocrystals Intimately and Permanently Connected with Polymers

DTIC Science & Technology

2016-04-21

Nanocrystals Intimately and Permanently Connected with Polymers Zhiqun Lin GEORGIA TECH RESEARCH CORPORATION Final Report 04/21/2016 DISTRIBUTION A...Connected with Polymers 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA9550-13-1-0101 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Lin, Zhiqun 5d. PROJECT...and properties, which are intimately and permanently capped by polymers on their surface (i.e., forming organic-inorganic nanocomposites), by

Polymerization speed and diffractive experiments in polymer network LC test cells

NASA Astrophysics Data System (ADS)

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

2018-02-01

Polymer-network liquid crystals (LCs), where the response properties of a LC can be enhanced by the presence of a porous polymer network, are investigated. In the reported experiments, liquid crystals were doped with a small amount (< 10%) of photo-curable acrylate monomers. Samples with surface grafted photoinitiators, dissolvable photoinitiators, and samples with both kinds of photoinitiators were prepared. Both conventional (planar electrodes) and diffractive (interdigitated electrodes) test cells were used. These samples were exposed with a UV light source and changes of their capacitance were investigated with an LCR meter during exposure. Due to the presence of the in-situ generated polymer network, the electro-optic response properties of photo cured samples were enhanced. For example, their continuous phase modulation properties led to more localized responses in samples with interdigitated electrodes, which caused suppression of selected diffraction orders in the diffraction patterns recorded in polymer network LC samples. Moreover, capacitance changes were investigated during photopolymerization of a blue phase LC.

Effect of surface treatments on physicomechanical, stain-resist, and UV protection properties of wool fabrics

NASA Astrophysics Data System (ADS)

Hassan, Mohammad M.; Leighs, Samuel J.

2017-10-01

The surface of wool fabrics is frequently modified to make them shrink-resistant, water repellent and also to improve their handle properties. In this work, we investigated the effect of common surface modification treatments on fabric stain-resistance, hydrophilicity and UV absorption performance. The surface of wool fabrics was modified by chlorination and also by reacting the chlorinated wool fabrics with a polyamide, a fibre-reactive amino-functional siloxane and a fluorocarbon polymer. The surface of the various treated fabrics was characterised by ATR-FTIR, contact angle measurement and scanning electron microscopy. The effect of surface modification on the tensile strength, surface hydrophilicity, stain-resistance, and UV absorption capacity of the fabric was investigated. It was found that all the treatments except the treatment with the amino-functional siloxane polymer slightly improved the tensile strength of the fabric. The chlorination treatment and the treatment with the polyamide resin made the fabric hydrophilic, and fluorocarbon and silicone resin treatment made the fabric hydrophobic.

Determining heat loss from the surface of polymer films via modeling of experimental fluorescence thermometry

NASA Astrophysics Data System (ADS)

Firestone, Gabriel; Bochinski, Jason; Meth, Jeffrey; Clarke, Laura

Understanding of the heat transfer characteristics of a polymer during processing is critical to predicting and controlling the resulting properties and has been studied extensively in injection molding. As new methodologies for polymer processing are developed, such as photothermal heating, it is important to build an understanding of how heat transfer properties change under these novel conditions. By combining theoretical and experimental approaches, the thermal properties of photothermally heated polymer films were measured. The key idea is that by measuring the steady state temperature profile of a spot heated polymer film via a fluorescence probe (the temperature versus distance from the heated region) and fitting to a theoretical model, heat transfer coefficients can be extracted. We apply this approach to three different polymer systems, crosslinked epoxy, poly(methyl methacrylate) and poly(ethylene oxide) thin films with a range of thicknesses, under different heating laser intensities and with different resultant temperatures. We will discuss the resultant trends and extension of the model beyond a simple spot heating configuration. Support from National Science Foundation CMMI-1069108 and CMMI-1462966.

A novel approach for application of nylon membranes in the biosensing domain

NASA Astrophysics Data System (ADS)

Farahmand, Elham; Ibrahim, Fatimah; Hosseini, Samira; Rothan, Hussin A.; Yusof, Rohana; Koole, Leo H.; Djordjevic, Ivan

2015-10-01

In this paper we report the polymer-coated microporous nylon membranes and their application as platforms for protein immobilization and subsequent detection of the dengue virus (DV) in blood serum. Protein recognition experiments were performed with enzyme-linked immunosorbent assay (ELISA). The polymers used for coatings were synthesized by free-radical polymerization reaction between methyl methacrylate (MMA) and methacrylic acid (MAA) in different concentrations. The MAA monomer has carefully been chosen to generate polymers with pendant carboxyl (-COOH) groups, which also exist on polymer surfaces. A high degree of control over surface-exposed -COOH groups has been achieved through variation of monomers concentration in polymerization reaction. The general aspect of this work relies on the dengue antibody (Ab) immobilization on surface -COOH groups via physical attachment or covalent immobilization. Prior to Ab immobilization and ELISA experiment, polymer-coated nylon samples were analyzed in detail for their physical properties by atomic force microscopy (AFM), scanning electron microscopy (SEM), and water-in-air contact angle (WCA) measurements. Membranes were further analyzed by Fourier transform infrared spectroscopy (FTIR) in order to establish the relationship between wettability, porosity, and surface roughness with chemical composition and concentration of -COOH groups on the coating's surface. Optimized coatings have shown high sensitivity towards dengue Ab molecules, revealing fundamental aspect of polymer-protein interfaces as a function of surface -COOH groups' concentration.

Fabrication of an SPR Sensor Surface with Antifouling Properties for Highly Sensitive Detection of 2,4,6-Trinitrotoluene Using Surface-Initiated Atom Transfer Polymerization

PubMed Central

Yatabe, Rui; Onodera, Takeshi; Toko, Kiyoshi

2013-01-01

In this study, we modified a surface plasmon resonance immunosensor chip with a polymer using surface-initiated atom transfer polymerization (SI-ATRP) for the highly sensitive detection of 2,4,6-trinitrotoluene (TNT). To immobilize a TNT analogue on the polymer, mono-2-(methacryloyloxy)ethylsuccinate (MES), which has a carboxyl group, was used in this study. However, the anti-TNT antibody may adsorb non-specifically on the polymer surface by an electrostatic interaction because MES is negatively charged. Therefore, a mixed monomer with MES and diethylaminoethylmethacrylate (DEAEM), which has a tertiary amino group and is positively charged, was prepared to obtain electroneutrality for suppressing the nonspecific adsorption. The detection of TNT was performed by inhibition assay using the polymer surface. To ensure high sensitivity to TNT, the affinity between the surface and the antibody was optimized by controlling the density of the initiator for ATRP by mixing two types of self-assembled monolayer reagents. As a result, a limit of detection of 5.7 pg/mL (ppt) for TNT was achieved using the optimized surface. PMID:23877126

Effect of Variation in Viscosity Grade of Ethycellulose on Theophylline Microcapsule Properties Prepared by Emulsion Solvent Evaporation.

PubMed

Garekani, Hadi Afrasiabi; Ahmadi, Behzad; Sadeghi, Fatemeh

2017-01-01

There are conflicting reports regarding the effect of polymer viscosity grade on microcapsule properties. The aim of the present study was to investigate the effect of just viscosity grade of ethylcellulose (EC) (not polymeric solution) on properties of theophylline microcapsules prepared by emulsion solvent evaporation. The effect of EC viscosity grade and drug:polymer ratio was investigated on microcapsule properties (yield, particle size, morphology, surface characteristics and drug release). Differential scanning calorimetry (DSC) and X-ray powder diffraction (XRD) were implemented to study the interaction and solid state of drug. The microcapsules were compressed in the presence of excipients and drug release was evaluated. The yield of microencapsulation and encapsulation efficiency at 1:1 drug:polymer ratio was dependent on EC viscosity. Microcapsules were spherical with some pores on their surfaces. The number of pores was more and their size was bigger for EC 100 cP microcapsules. Theophylline remained in crystalline form after encapsulation. DSC studies confirmed lack of interaction between drug and polymer. The drug release was rapid at 2:1 drug:polymer whilst it was slowed down at 1:1 drug:polymer ratio. Microcapsules obtained from EC 100 cP showed slightly faster drug release at latter ratio. Marginal changes in release rate were observed after compression of microcapsules. All viscosity grades of EC were able to sustain the release of the drug from microcapsules. Considering the similar release profiles for microcapsules prepared from different viscosities of EC, the use of lower viscosity grade of EC is recommended due to the ease of production and also less processing time. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Vacuum-based surface modification of organic and metallic substrates

NASA Astrophysics Data System (ADS)

Torres, Jessica

Surface physico-chemical properties play an important role in the development and performance of materials in different applications. Consequently, understanding the chemical and physical processes involved during surface modification strategies is of great scientific and technological importance. This dissertation presents results from the surface modification of polymers, organic films and metallic substrates with reactive species, with the intent of simulating important modification processes and elucidating surface property changes of materials under different environments. The reactions of thermally evaporated copper and titanium with halogenated polytetrafluoroethylene (PTFE) and polyvinyl chloride (PVC) are used to contrast the interaction of metals with polymers. Results indicate that reactive metallization is thermodynamically favored when the metal-halogen bond strength is greater than the carbon-halogen bond strength. X-ray post-metallization treatment results in an increase in metal-halide bond formation due to the production of volatile halogen species in the polymer that react with the metallic overlayer. The reactions of atomic oxygen (AO) and atomic chlorine with polyethylene (PE) and self-assembled monolayers (SAMs) films were followed to ascertain the role of radical species during plasma-induced polymer surface modification. The reactions of AO with X-ray modified SAMs are initially the dominated by the incorporation of new oxygen containing functionality at the vacuum/film interface, leading to the production of volatile carbon containing species such as CO2 that erodes the hydrocarbon film. The reaction of atomic chlorine species with hydrocarbon SAMs, reveals that chlorination introduces C-Cl and C-Cl2 functionalities without erosion. A comparison of the reactions of AO and atomic chlorine with PE reveal a maximum incorporation of the corresponding C-O and C-Cl functionalities at the polymer surface. A novel method to prepare phosphorous-containing polymer surfaces through ion implantation of trimethyl phosphine onto PE is presented. Air exposure of the resulting P-implanted PE leads to the surface selective oxidation of phosphorous moieties. P-containing hydrocarbon films are used to model the surface chemical changes of P-containing polymers exposed to AO. Results indicate that oxidized phosphorous species protect the film from AO-induced erosion. The low temperature (<150 K) oxidation of nitrided iron surfaces exposed to oxygen reveal the formation of iron oxynitride (FexNyO z, nitrosonium ions (NO+) as well as nitrite/nitrito and nitrate type species. The production of nitrite/nitrito and nitrate species is taken as evidence for the existence of oxygen insertion chemistry into the iron nitride lattice under these low temperature oxidation conditions. Upon annealing the oxidized iron nitride surface, nitrogen desorbs exclusively as nitric oxide (NO).

Silicon containing electroconductive polymers and structures made therefrom

NASA Technical Reports Server (NTRS)

Nagasubramanian, Ganesan (Inventor); Distefano, Salvador (Inventor); Liang, Ranty H. (Inventor)

1991-01-01

An electropolymerized film comprised of polymers and copolymers of a monomer is formed on the surface of an anode. The finished structures have superior electrical and mechanical properties for use in applications such as electrostatic dissipation and for the reduction of the radar cross section of advanced aircraft.

Water Vapor Permeation of Metal Oxide/Polymer Coated Plastic Films

NASA Astrophysics Data System (ADS)

Numata, Yukihiro; Oya, Toshiyuki; Kuwahara, Mitsuru; Ito, Katsuya

Barrier performance to water vapor permeation of ceramic coated layers deposited on flexible polymer films is of great interest to food packaging, medical device packaging and flat panel display industries. In this study, a new type film in which a ceramic layer is deposited on a polymer coated film was proposed for lower water vapor permeation. It is important how to control interfacial properties between each layer and film for good barrier performance. Several kinds of polymer coated materials were prepared for changing surface free energy of the films before and after depositing the ceramic layer. The ceramic layer, which is composed of mixed material of SiO2 and Al2O3, was adopted under the same conditions. The following results were obtained; 1) Water vapor permeation is not related to the surface energy of polymer coated films, 2) After depositing the ceramic layer, however, a strong correlation is observed between the water vapor permeation and surface free energy. 3) The phenomenon is considered that the polarity of the polymer layers plays a key role in changing the structure of ceramic coated layers.

Influence of continuous magnetic field on the separation of ephedrine enantiomers by molecularly imprinted polymers.

PubMed

Guerreiro, António R; Korkhov, Vadim; Mijangos, Irene; Piletska, Elena V; Rodins, Juris; Turner, Anthony P F; Piletsky, Sergey A

2008-02-28

A set of polymers was imprinted with (-)-ephedrine using UV initiation, under the influence of a constant external magnetic field with intensities ranging from 0 to 1.55 T. Synthesised materials were characterised by X-ray crystallography, infrared spectroscopy, swelling and surface area. Recognition properties were assessed by the ability to discriminate between (+) and (-)-ephedrine and by Scatchard analyses on chromatographic mode. It was shown that polymer morphology and recognition properties are affected by the magnetic field. This resulted in considerable improvements in the chromatographic resolution of ephedrine enantiomers by materials synthesised under the influence of magnetic field. Apparently the magnetic field improved the ordering of the polymer structure and facilitated the formation of more uniform imprinting sites.

Optical waveguiding properties of colloidal quantum dots doped polymer microfibers.

PubMed

Yu, Jiahao; Wang, Xiongbin; Chen, Rui

2018-05-14

QDs-doped polymer microfibers are fabricated through direct drawing method. By adding the polymethylmethacrylate into polystyrene, the surface quality and flexibility of microfiber are improved. Under direct excitation by the focused laser, the polymer microfibers doped with different quantum dots emit different colors and act as an optical waveguide. The waveguide properties of the microfiber are studied in detail. It is found that refractive index of the substrate and diameter of microfiber are the most important factors that affect the optical loss of this waveguide. The microfiber does not produce significant polarization after being deposited on the substrate. Moreover, exciting the QDs-doped polymer microfiber through a blue LED is demonstrated. This structure may find widespread applications in integrated photonic devices.

Adsorbed Polymer Nanolayers on Solids: Mechanism, Structure and Applications

NASA Astrophysics Data System (ADS)

Sen, Mani Kuntal

In this thesis, by combining various advanced x-ray scattering, spectroscopic and other surface sensitive characterization techniques, I report the equilibrium polymer chain conformations, structures, dynamics and properties of polymeric materials at the solid-polymer melt interfaces. Following the introduction, in chapter 2, I highlight that the backbone chains (constituted of CH and CH2 groups) of the flattened polystyrene (PS) chains preferentially orient normal to the weakly interactive substrate surface via thermal annealing regardless of the initial chain conformations, while the orientation of the phenyl rings becomes randomized, thereby increasing the number of surface-segmental contacts (i.e., enthalpic gain) which is the driving force for the flattening process of the polymer chains even onto a weakly interactive solid. In chapter 3, I elucidate the flattened structures in block copolymer (BCP) thin films where both blocks lie flat on the substrate, forming a 2D randomly phase-separated structure irrespective of their microdomain structures and interfacial energetics. In chapter 4, I reveal the presence of an irreversibly adsorbed BCP layer which showed suppressed dynamics even at temperatures far above the individual glass transition temperatures of the blocks. Furthermore, this adsorbed BCP layer plays a crucial role in controlling the microdomain orientation in the entire film. In chapter 5, I report a radically new paradigm of designing a polymeric coating layer of a few nanometers thick ("polymer nanolayer") with anti-biofouling properties.

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.

Engineering the Mechanical Properties of Polymer Networks with Precise Doping of Primary Defects.

PubMed

Chan, Doreen; Ding, Yichuan; Dauskardt, Reinhold H; Appel, Eric A

2017-12-06

Polymer networks are extensively utilized across numerous applications ranging from commodity superabsorbent polymers and coatings to high-performance microelectronics and biomaterials. For many applications, desirable properties are known; however, achieving them has been challenging. Additionally, the accurate prediction of elastic modulus has been a long-standing difficulty owing to the presence of loops. By tuning the prepolymer formulation through precise doping of monomers, specific primary network defects can be programmed into an elastomeric scaffold, without alteration of their resulting chemistry. The addition of these monomers that respond mechanically as primary defects is used both to understand their impact on the resulting mechanical properties of the materials and as a method to engineer the mechanical properties. Indeed, these materials exhibit identical bulk and surface chemistry, yet vastly different mechanical properties. Further, we have adapted the real elastic network theory (RENT) to the case of primary defects in the absence of loops, thus providing new insights into the mechanism for material strength and failure in polymer networks arising from primary network defects, and to accurately predict the elastic modulus of the polymer system. The versatility of the approach we describe and the fundamental knowledge gained from this study can lead to new advancements in the development of novel materials with precisely defined and predictable chemical, physical, and mechanical properties.

Visualization of Au Nanoparticles Buried in a Polymer Matrix by Scanning Thermal Noise Microscopy.

PubMed

Yao, Atsushi; Kobayashi, Kei; Nosaka, Shunta; Kimura, Kuniko; Yamada, Hirofumi

2017-02-17

Several researchers have recently demonstrated visualization of subsurface features with a nanometer-scale resolution using various imaging schemes based on atomic force microscopy. Since all these subsurface imaging techniques require excitation of the oscillation of the cantilever and/or sample surface, it has been difficult to identify a key imaging mechanism. Here we demonstrate visualization of Au nanoparticles buried 300 nm into a polymer matrix by measurement of the thermal noise spectrum of a microcantilever with a tip in contact to the polymer surface. We show that the subsurface Au nanoparticles are detected as the variation in the contact stiffness and damping reflecting the viscoelastic properties of the polymer surface. The variation in the contact stiffness well agrees with the effective stiffness of a simple one-dimensional model, which is consistent with the fact that the maximum depth range of the technique is far beyond the extent of the contact stress field.

[Preparation and evaluation of novel mesoporous molecular sieve of baicalin surface molecularly imprinted polymers].

PubMed

Gu, Xia-li; He, Hong-liang; Shi, Li-ying; Gao, Yan-kun; Chen, Li-na

2015-05-01

Taking mesoporous molecular sieve MCM-41 as a substrate, baicalin (BA) as template, acrylamide (AM) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent, ethanol as solvent, under thermal polymerization initiator of azobis isobutyronitrilo (AIBN) , a kind of selective recognition of baicalin surface molecularly imprinted polymer was synthesized. The surface morphologies and characteristics of the MIPs were characterized by infrared spectroscopy (IR) and transmission electron microscope (TEM). The adsorption properties of polymer microsphere for the template were tested by the dynamic adsorption equilibrium experiments and static adsorption equilibrium experiments. The experiment showed that the imprinting process was successfully and the well-ordered one-dimensional pore structure of MCM-41 was still preserved. Furthermore, molecularly imprinted polymers had higher selective ability for BA, then provided a new method for the efficient separation and enrichment of baicalin active ingredients from medicinal plants Scutellaria baicalensis.

Solution and interfacial behavior of modified silicone polymers and their interactions with solid substrates

NASA Astrophysics Data System (ADS)

Purohit, Parag

Surface treatment is very important step in many applications such as fabric finishing, coatings, cosmetics and personal care. Silicone polymers are a class of organic/inorganic materials that show unique properties such as weak intermolecular forces and high flexibility enabling even a very high molecular weight chain to achieve optimal orientation on surfaces. Material properties such as softness, repellency, bounciness and friction can therefore be tailored by using appropriately modified silicone polymers. Despite wide applications, the underlying mechanisms of material modification are unknown and tailoring silicones for applications remains mostly empirical. Thus the objective of this research is to understand the solution and interfacial behavior of functionalized silicone polymers, which govern their performance in material modification. Modified silicones are simultaneously hydrophobic and oleophobic in nature and due to this nearly universal non-compatibility, the studies of these polymers present unusual challenges. Due to this incompatible nature, the functionalized silicone polymers were emulsified into O/W emulsions to study their solution and interfacial properties. The colloidal properties such as electrokinetic and droplet distribution of these emulsions are assumed to play an important role in the observed surface and physical properties of solid substrates (in present study, cellulosic substrates) as well the stability of emulsions itself. To understand the effects of modified silicones on cellulosic substrates a variety of techniques such as frictional analysis, scanning electron microscopy and atomic force microscopy that can probe from macro to nano level were used. It is hypothesized that the size distribution and charge of silicone emulsions as well as the physiochemical conditions such as pH, control silicone conformation which in turn affect the modification of the substrate properties. With bimodal droplet distribution of silicone emulsions, the nano-sized droplets can penetrate deeper into the substrate to provide bounciness, whereas macro-sized droplets can coat the top layer leading to friction reduction. It was observed that at pH 5.5 the silicone treatment resulted in charge reversal of fibers as opposed to treatment at pH 9.5. On a macroscopic scale 20% reduction in frictional coefficient of the fabric was observed after treatment with quaternized (cationically modified) silicones as compared to untreated fibers. It was also observed using AFM that the fibrils treated with quaternized silicones are uniform, well stacked and smoother than the untreated fibers. Spectroscopic analysis of treated fibers using Raman spectroscopy indicated a decrease in fiber stress as a function of modification of silicone polymer and the interaction pH. It is concluded that the protonated amine functional silicone (below pH 7) as well as the quaternized silicone interacts with the negatively charged cellulose fibers primarily through electrostatic interactions. It is proposed that this initial surface coating is a uniform thin film which allows further deposition of polymer from the emulsion. It was observed that at high pH the zetapotential of silicone emulsions decreases drastically and the nano emulsions turn turbid. It is proposed that the observed electrophoretic and nephelometric behavior at high pH is due to flocculation of nanosized droplets to micron size, which eventually leads to droplets coalescing and emulsion destabilization. It is also postulated that the nano emulsion possess a critical dilution concentration (CDC), above which dilution leads to rapid coalescence. This critical dilution phase was further confirmed through polarity parameter and excimer formation studies which show significantly different polymer and surfactant microstructures near the CDC. Hence it is concluded that the observed surface properties of the substrate obtained above the CDC are significantly different than those below the CDC. The results reveal the vital role of physiochemical parameters such as pH, droplet size, and concentration on the emulsion stability as well as the observed physical/chemical properties of the substrates.

Nanocellulose in Polymer Composites and Biomedical: Research and Applications

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

Lu, Yuan; Tekinalp, Halil L; Peter, William H

Nanocellulose materials are nano-sized cellulose fibers or crystals that are produced by bacteria or derived from plants. These materials exhibit exceptional strength characteristics, light weight, transparency, and excellent biocompatibility. Compared to some other nanomaterials, nanocellulose is renewable and less expensive to produce. As such, a wide range of applications for nanocellulose has been envisioned. Most extensively studied areas include polymer composites and biomedical applications. Cellulose nanofibrils and nanocrystals have been used to reinforce both thermoplastic and thermoset polymers. Given the hydrophilic nature of these materials, the interfacial properties with most polymers are often poor. Various surface modification procedures have thusmore » been adopted to improve the interaction between polymer matrix and cellulose nanofibrils or nanocrystals. In addition, the applications of nanocellulose as biomaterials have been explored including wound dressing, tissue repair, and medical implants. Nanocellulose materials for wound healing and periodontal tissue recovery have become commercially available, demonstrating the great potential of nanocellulose as a new generation of biomaterials. In this review, we highlight the applications of nanocellulose as reinforcing fillers for composites and the effect of surface modification on the mechanical properties as well as the application as biomaterials.« less

Simulated Space Vacuum Ultraviolet (VUV) Exposure Testing for Polymer Films

NASA Technical Reports Server (NTRS)

Dever, Joyce A.; Pietromica, Anthony J.; Stueber, Thomas J.; Sechkar, Edward A.; Messer, Russell K.

2002-01-01

Vacuum ultraviolet (VUV) radiation of wavelengths between 115 and 200 nm produced by the sun in the space environment can cause degradation to polymer films producing changes in optical, mechanical, and chemical properties. These effects are particularly important for thin polymer films being considered for ultra-lightweight space structures, because, for most polymers, VUV radiation is absorbed in a thin surface layer. NASA Glenn Research Center has developed facilities and methods for long-term ground testing of polymer films to evaluate space environmental VUV radiation effects. VUV exposure can also be used as part of sequential simulated space environmental exposures to determine combined damaging effects. This paper will describe the effects of VUV on polymer films and the necessity for ground testing. Testing practices used at Glenn Research Center for VUV exposure testing will be described including characterization of the VUV radiation source used, calibration procedures traceable to the National Institute of Standards and Technology (NIST), and testing techniques for VUV exposure of polymer surfaces.

Water at surfaces with tunable surface chemistries

NASA Astrophysics Data System (ADS)

Sanders, Stephanie E.; Vanselous, Heather; Petersen, Poul B.

2018-03-01

Aqueous interfaces are ubiquitous in natural environments, spanning atmospheric, geological, oceanographic, and biological systems, as well as in technical applications, such as fuel cells and membrane filtration. Where liquid water terminates at a surface, an interfacial region is formed, which exhibits distinct properties from the bulk aqueous phase. The unique properties of water are governed by the hydrogen-bonded network. The chemical and physical properties of the surface dictate the boundary conditions of the bulk hydrogen-bonded network and thus the interfacial properties of the water and any molecules in that region. Understanding the properties of interfacial water requires systematically characterizing the structure and dynamics of interfacial water as a function of the surface chemistry. In this review, we focus on the use of experimental surface-specific spectroscopic methods to understand the properties of interfacial water as a function of surface chemistry. Investigations of the air-water interface, as well as efforts in tuning the properties of the air-water interface by adding solutes or surfactants, are briefly discussed. Buried aqueous interfaces can be accessed with careful selection of spectroscopic technique and sample configuration, further expanding the range of chemical environments that can be probed, including solid inorganic materials, polymers, and water immiscible liquids. Solid substrates can be finely tuned by functionalization with self-assembled monolayers, polymers, or biomolecules. These variables provide a platform for systematically tuning the chemical nature of the interface and examining the resulting water structure. Finally, time-resolved methods to probe the dynamics of interfacial water are briefly summarized before discussing the current status and future directions in studying the structure and dynamics of interfacial water.

Reactive polymer coatings: A robust platform towards sophisticated surface engineering for biotechnology

NASA Astrophysics Data System (ADS)

Chen, Hsien-Yeh

Functionalized poly(p-xylylenes) or so-called reactive polymers can be synthesized via chemical vapor deposition (CVD) polymerization. The resulting ultra-thin coatings are pinhole-free and can be conformally deposited to a wide range of substrates and materials. More importantly, the equipped functional groups can served as anchoring sites for tailoring the surface properties, making these reactive coatings a robust platform that can deal with sophisticated challenges faced in biointerfaces. In this work presented herein, surface coatings presenting various functional groups were prepared by CVD process. Such surfaces include aldehyde-functionalized coating to precisely immobilize saccharide molecules onto well-defined areas and alkyne-functionalized coating to click azide-modified molecules via Huisgen 1,3-dipolar cycloaddition reaction. Moreover, CVD copolymerization has been conducted to prepare multifunctional coatings and their specific functions were demonstrated by the immobilization of biotin and NHS-ester molecules. By using a photodefinable coating, polyethylene oxides were immobilized onto a wide range of substrates through photo-immobilization. Spatially controlled protein resistant properties were characterized by selective adsorption of fibrinogen and bovine serum albumin as model systems. Alternatively, surface initiator coatings were used for polymer graftings of polyethylene glycol) methyl ether methacrylate, and the resultant protein- and cell- resistant properties were characterized by adsorption of kinesin motor proteins, fibrinogen, and murine fibroblasts (NIH3T3). Accessibility of reactive coatings within confined microgeometries was systematically studied, and the preparation of homogeneous polymer thin films within the inner surface of microchannels was demonstrated. Moreover, these advanced coatings were applied to develop a dry adhesion process for microfluidic devices. This process provides (i) excellent bonding strength, (ii) extended storage time prior to bonding, and (iii) well-defined surface functionalities for subsequent surface modifications. Finally, we have also prepared surface microstructures and surface patterns using reactive coatings via photopatterning, projection lithography, supramolecular nanostamping (SuNS), and vapor-assisted micropatterning in replica structures (VAMPIR). These patterning techniques can be complimentarily used and provide access to precisely confined microenvironments on flat and curved geometries. Reactive coatings provide a technology platform that creates active, long-term control and may lead to improved mimicry of biological systems for effective bio-functional modifications.

Poly(ferulic acid-co-tyrosine): Effect of the Regiochemistry on the Photophysical and Physical Properties en Route to Biomedical Applications

PubMed Central

2015-01-01

The photophysical and mechanical properties of novel poly(carbonate-amide)s derived from two biorenewable resources, ferulic acid (FA) and l-tyrosine ethyl ester, were evaluated in detail. From these two bio-based precursors, a series of four monomers were generated (having amide and/or carbonate coupling units with remaining functionalities to allow for carbonate formation) and transformed to a series of four poly(carbonate-amide)s. The simplest monomer, which was biphenolic and was obtained in a single amidation synthetic step, displayed bright, visible fluorescence that was twice brighter than FA. Multidimensional fluorescence spectroscopy of the polymers in solution highlighted the strong influence that regioselectivity and the degree of polymerization have on their photophysical properties. The regiochemistry of the system had little effect on the wettability, surface free energy, and Young’s modulus (ca. 2.5 GPa) in the solid state. Confocal imaging of solvent-cast films of each polymer revealed microscopically flat surfaces with fluorescent emission deep into the visible region. Fortuitously, one of the two regiorandom polymers (obtainable from the biphenolic monomer in only an overall two synthetic steps from FA and l-tyrosine ethyl ester) displayed the most promising fluorescent properties both in the solid state and in solution, allowing for the possibility of translating this system as a self-reporting or imaging agent in future applications. To further evaluate the potential of this polymer as a biodegradable material, hydrolytic degradation studies at different pH values and temperatures were investigated. Additionally, the antioxidant properties of the degradation products of this polymer were compared with its biphenolic monomer and FA. PMID:25364040

Surface dynamics of amorphous polymers used for high-voltage insulators.

PubMed

Shemella, Philip T; Laino, Teodoro; Fritz, Oliver; Curioni, Alessandro

2011-11-24

Amorphous siloxane polymers are the backbone of high-voltage insulation materials. The natural hydrophobicity of their surface is a necessary property for avoiding leakage currents and dielectric breakdown. As these surfaces are exposed to the environment, electrical discharges or strong mechanical impact can temporarily destroy their water-repellent properties. After such events, however, a self-healing process sets in and restores the original hydrophobicity within some hours. In the present study, we investigate possible mechanisms of this restoration process. Using large-scale, all-atom molecular dynamics simulations, we show that molecules on the material surface have augmented motion that allows them to rearrange with a net polarization. The overall surface region has a net orientation that contributes to hydrophobicity, and charged groups that are placed at the surface migrate inward, away from the vacuum interface and into the bulk-like region. Our simulations provide insight into the mechanisms for hydrophobic self-recovery that repair material strength and functionality and suggest material compositions for future high-voltage insulators. © 2011 American Chemical Society

Water adsorption on surface-modified cellulose nanocrystals

NASA Astrophysics Data System (ADS)

Wei, Zonghui; Sinko, Robert; Keten, Sinan; Luijten, Erik

Cellulose nanocrystals (CNCs) have attracted much attention as a filler phase for polymer nanocomposites due to their impressive mechanical properties, low cost, and environmental sustainability. Despite their promise for this application, there are still numerous obstacles that prevent optimal performance of CNC-polymer nanocomposites, such as poor filler dispersion and high levels of water absorption. One way to mitigate these negative effects is to modify CNC surfaces. Computational approaches can be utilized to obtain direct insight into the properties of modified CNC surfaces and probe the interactions of CNCs with other materials to facilitate the experimental design of nanocomposites. We use atomistic grand-canonical Monte Carlo simulations to study how surface modification of ion-exchanged sulfated cellulose nanocrystals (Na-CNCs) impacts water adsorption. We find that methyl(triphenyl)phosphonium-exchanged CNCs adsorb less water than Na-CNCs at the same relative humidity, supporting recent experimental dynamic vapor sorption measurements. By characterizing the distribution and configuration of water molecules near the modified CNC surfaces we determine how surface modifications disrupt CNC-water interactions.

Interphase and particle dispersion correlations in polymer nanocomposites

NASA Astrophysics Data System (ADS)

Senses, Erkan

Particle dispersion in polymer matrices is a major parameter governing the mechanical performance of polymer nanocomposites. Controlling particle dispersion and understanding aging of composites under large shear and temperature variations determine the processing conditions and lifetime of composites which are very important for diverse applications in biomedicine, highly reinforced materials and more importantly for the polymer composites with adaptive mechanical responses. This thesis investigates the role of interphase layers between particles and polymer matrices in two bulk systems where particle dispersion is altered upon deformation in repulsive composites, and good-dispersion of particles is retained after multiple oscillatory shearing and aging cycles in attractive composites. We demonstrate that chain desorption and re-adsorption processes in attractive composites under shear can effectively enhance the bulk microscopic mechanical properties, and long chains of adsorbed layers lead to a denser entangled interphase layer. We further designed experiments where particles are physically adsorbed with bimodal lengths of homopolymer chains to underpin the entanglement effect in interphases. Bimodal adsorbed chains are shown to improve the interfacial strength and used to modulate the elastic properties of composites without changing the particle loading, dispersion state or polymer conformation. Finally, the role of dynamic asymmetry (different mobilities in polymer blends) and chemical heterogeneity in the interphase layer are explored in systems of poly(methyl methacrylate) adsorbed silica nanoparticles dispersed in poly(ethylene oxide) matrix. Such nanocomposites are shown to exhibit unique thermal-stiffening behavior at temperatures above glass transitions of both polymers. These interesting findings suggest that the mobility of the surface-bound polymer is essential for reinforcement in polymer nanocomposites, contrary to existing glassy layer theories for polymers on attractive particle surfaces. The shown thermally-induced stiffening behavior is reversible and makes this interfacial mechanism highly attractive in developing new active, remotely controllable engineered materials from non-responsive components.

Polyhedral Oligomeric Silsesquioxane (POSS)-Containing Polymer Nanocomposites

PubMed Central

Ayandele, Ebunoluwa; Sarkar, Biswajit; Alexandridis, Paschalis

2012-01-01

Hybrid materials with superior structural and functional properties can be obtained by incorporating nanofillers into polymer matrices. Polyhedral oligomeric silsesquioxane (POSS) nanoparticles have attracted much attention recently due to their nanometer size, the ease of which these particles can be incorporated into polymeric materials and the unique capability to reinforce polymers. We review here the state of POSS-containing polymer nanocomposites. We discuss the influence of the incorporation of POSS into polymer matrices via chemical cross-linking or physical blending on the structure of nanocomposites, as affected by surface functional groups, and the POSS concentration. PMID:28348318

Biocompatible polymer coating of titania nanotube arrays for improved drug elution and osteoblast adhesion.

PubMed

Gulati, Karan; Ramakrishnan, Saminathan; Aw, Moom Sinn; Atkins, Gerald J; Findlay, David M; Losic, Dusan

2012-01-01

Bacterial infection, extensive inflammation and poor osseointegration have been identified as the major reasons for [early] orthopaedic implant failures based on titanium. Creating implants with drug-eluting properties to locally deliver drugs is an appealing way to address some of these problems. To improve properties of titanium for orthopaedic applications, this study explored the modification of titanium surfaces with titaniananotube (TNT) arrays, and approach that combines drug delivery into bone and potentially improved bone integration. A titania layer with an array of nanotube structures (∼120 nm in diameter and 50 μm in length) was synthesized on titanium surfaces by electrochemical anodization and loaded with the water-insoluble anti-inflammatory drug indomethacin. A simple dip-coating process of polymer modification formed thin biocompatible polymer films over the drug-loaded TNTs to create TNTs with predictable drug release characteristics. Two biodegradable and antibacterial polymers, chitosan and poly(lactic-co-glycolic acid), were tested for their ability to extend the drug release time of TNTs and produce favourable bone cell adhesion properties. Dependent on polymer thickness, a significant improvement in the drug release characteristics was demonstrated, with reduced burst release (from 77% to >20%) and extended overall release from 4 days to more than 30 days. Excellent osteoblast adhesion and cell proliferation on polymer-coated TNTs compared with uncoated TNTs were also observed. These results suggest that polymer-modified implants with a TNT layer are capable of delivering a drug to a bone site over an extended period and with predictable kinetics. In addition, favourable bone cell adhesion suggests that such an implant would have good biocompatibility. The described approach is broadly applicable to a wide range of drugs and implants currently used in orthopaedic practice. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.

Atomistic simulations of bulk, surface and interfacial polymer properties

NASA Astrophysics Data System (ADS)

Natarajan, Upendra

In chapter I, quasi-static molecular mechanics based simulations are used to estimate the activation energy of phenoxy rings flips in the amorphous region of a semicrystalline polyimide. Intra and intermolecular contributions to the flip activation energy, the torsional cooperativity accompanying the flip, and the effect of the flip on the motion in the glassy bulk state, are looked at. Also, comparison of the weighted mean activation energy is made with experimental data from solid state NMR measurements; the simulated value being 17.5 kcal/mol., while the experimental value was observed to be 10.5 kcal/mol. Chapter II deals with construction of random copolymer thin films of styrene-butadiene (SB) and styrene-butadiene-acrylonitrile (SBA). The structure and properties of the free surfaces presented by these thin films are analysed by, the atom mass density profiles, backbone bond orientation function, and the spatial distribution of acrylonitrile groups and styrene rings. The surface energies of SB and SBA are calculated using an atomistic equation and are compared with experimental data in the literature. In chapter III, simulations of polymer-polymer interfaces between like and unlike polymers, specifically cis-polybutadiene (PBD) and atatic polypropylene (PP), are presented. The structure of an incompatible polymer-polymer interface, and the estimation of the thermodynamic work of adhesion and interfacial energy between different incompatible polymers, form the focus here. The work of adhesion is calculated using an atomistic equation and is further used in a macroscopic equation to estimate the interfacial energy. The interfacial energy is compared with typical values for other immiscible systems in the literature. The interfacial energy compared very well with interfacial energy values for a few other immiscible hydrocarbon pairs. In chapter IV, the study proceeds to look at the interactions between nonpolar and polar small molecules with SB and SBA thin film surfaces. Toluene, hexadecane and water molecules are separately simulated to interact with SB and SBA surfaces in vacuum. The energetics of interaction are calculated atomistically and used in the atomistic equation to calculate the interfacial energy or the interaction energy. Comparisons with experimental data are not made due to the small concentrations of the molecules on the polymer surface. However, fundamental understanding of the structure of the system and the breakup of the energetics are provided by such a study.

Directed Self-Assembly in "Breath Figure" Templating of Melamine-Based Amphiphilic Copolymers: Effect of Hydrophilic End-Chain on Honeycomb Film Formation and Wetting.

PubMed

Yin, Hongyao; Feng, Yujun; Billon, Laurent

2018-01-09

Amphiphilic copolymers are widely used in the fabrication of hierarchically honeycomb-structured films through a "breath figure" (BF) process because the hydrophilic block plays a key role in stabilising water templating. However, the hydrophilic monomers reported are mainly confined to acrylic acid and its derivatives, which largely limits understanding of the formation of BF arrays and the introduction of additional functions on porous films. The relationship between polymer composition, film microstructure and surface properties are also less documented. Herein, a novel melamine-based hydrophilic moiety, N-[3-({3-[(4,6-bis{[3-(dimethylamino)propyl]amino}-1,3,5-triazin-2yl)amino]propyl}(methyl)amino)propyl]methacrylamide (ANME), was incorporated into polystyrene (PS) chains by combining atom-transfer radical polymerisation and post-modification to afford three well-defined end-functionalised PS-PANME derivatives. These polymers were used to fabricate honeycomb films through the BF technique. Both inner and outer microstructures of the films were characterised by optical microscopy, AFM and SEM. Polymer hydrophilicity is enhanced upon increasing the PANME content, which results in variation of the film microstructure and porosity, and provokes a transition from Cassie-Baxter to Wenzel behaviour. Furthermore, the surface wettability of as-prepared honeycomb films and corresponding pillared films is mainly governed by film morphology, rather than by the properties of the polymers. Knowledge of the relationships between polymer composition and film structure, as well as surface wettability, is beneficial to design and prepare hierarchically porous films with desirable structures and properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sialic Acid-Responsive Polymeric Interface Material: From Molecular Recognition to Macroscopic Property Switching

NASA Astrophysics Data System (ADS)

Xiong, Yuting; Jiang, Ge; Li, Minmin; Qing, Guangyan; Li, Xiuling; Liang, Xinmiao; Sun, Taolei

2017-01-01

Biological systems that utilize multiple weak non-covalent interactions and hierarchical assemblies to achieve various bio-functions bring much inspiration for the design of artificial biomaterials. However, it remains a big challenge to correlate underlying biomolecule interactions with macroscopic level of materials, for example, recognizing such weak interaction, further transforming it into regulating material’s macroscopic property and contributing to some new bio-applications. Here we designed a novel smart polymer based on polyacrylamide (PAM) grafted with lactose units (PAM-g-lactose0.11), and reported carbohydrate-carbohydrate interaction (CCI)-promoted macroscopic properties switching on this smart polymer surface. Detailed investigations indicated that the binding of sialic acid molecules with the grafted lactose units via the CCIs induced conformational transformation of the polymer chains, further resulted in remarkable and reversible switching in surface topography, wettability and stiffness. With these excellent recognition and response capacities towards sialic acid, the PAM-g-lactose0.11 further facilitated good selectivity, strong anti-interference and high adsorption capacity in the capture of sialylated glycopeptides (important biomarkers for cancers). This work provides some enlightenment for the development of biointerface materials with tunable property, as well as high-performance glycopeptide enrichment materials.

Nanocomposites based on self-assembly poly(hydroxypropyl methacrylate)-block-poly(N-phenylmaleimide) and Fe3O4-NPs. Thermal stability, morphological characterization and optical properties

NASA Astrophysics Data System (ADS)

Pizarro, Guadalupe del C.; Marambio, Oscar G.; Jeria-Orell, Manuel; Sánchez, Julio; Oyarzún, Diego P.

2018-02-01

The current work presents the synthesis, characterization and preparation of organic-inorganic hybrid polymer films that contain inorganic magnetic nanoparticles (NPs). The block copolymer, prepared by Atom-Transfer Radical Polymerization (ATRP), was used as a nanoreactor for iron oxide NPs. The NPs were embedded in poly(hydroxypropyl methacrylate)-block-poly(N-phenylmaleimide) matrix. The following topographical modifications of the surface of the film were specially analyzed: control of pore features and changes in surface roughness. Finally, the NPs functionality inside the polymer matrix and how it may affect the thermal and optical properties of the films were assessed.

Dependence of nanomechanical modification of polymers on plasma-induced cross-linking

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

Tajima, S.; Komvopoulos, K.

2007-01-01

The nanomechanical properties of low-density polyethylene (LDPE) modified by inductively coupled, radio-frequency Ar plasma were investigated by surface force microscopy. The polymer surface was modified under plasma conditions of different ion energy fluences and radiation intensities obtained by varying the sample distance from the plasma power source. Nanoindentation results of the surface stiffness versus maximum penetration depth did not reveal discernible differences between untreated and plasma-treated LDPE, presumably due to the small thickness of the modified surface layer that resulted in a substrate effect. On the contrary, nanoscratching experiments demonstrated a significant increase in the surface shear resistance of plasma-modifiedmore » LDPE due to chain cross-linking. These experiments revealed an enhancement of cross-linking with increasing ion energy fluence and radiation intensity, and a tip size effect on the friction force and dominant friction mechanisms (adhesion, plowing, and microcutting). In addition, LDPE samples with a LiF crystal shield were exposed to identical plasma conditions to determine the role of vacuum ultraviolet (VUV) and ultraviolet (UV) radiation in the cross-linking process. The cross-linked layer of plasma-treated LDPE exhibited much higher shear strength than that of VUV/UV-treated LDPE. Plasma-induced surface modification of the nanomechanical properties of LDPE is interpreted in the context of molecular models of the untreated and cross-linked polymer surfaces derived from experimental findings.« less

Literature Review of Polymer Derived Ceramics

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

Peterson, Reuben James

2016-05-25

Polymer Derived Ceramics (PDCs), also known as preceramic polymers, are valuable coating agents that are used to produce surface barriers on substrates such as stainless steel. These barriers protect against a multitude of environmental threats, and have been used since their research and development in 19772. This paper seeks to review and demonstrate the remarkable properties and versatility that PDCs have to offer, while also giving a brief overview of the processing techniques used today.

Protein Corona Composition of Superparamagnetic Iron Oxide Nanoparticles with Various Physico-Chemical Properties and Coatings

NASA Astrophysics Data System (ADS)

Sakulkhu, Usawadee; Mahmoudi, Morteza; Maurizi, Lionel; Salaklang, Jatuporn; Hofmann, Heinrich

2014-05-01

Because of their biocompatibility and unique magnetic properties, superparamagnetic iron oxide nanoparticles NPs (SPIONs) are recognized as some of the most prominent agents for theranostic applications. Thus, understanding the interaction of SPIONs with biological systems is important for their safe design and efficient applications. In this study, SPIONs were coated with 2 different polymers: polyvinyl alcohol polymer (PVA) and dextran. The obtained NPs with different surface charges (positive, neutral, and negative) were used as a model study of the effect of surface charges and surface polymer materials on protein adsorption using a magnetic separator. We found that the PVA-coated SPIONs with negative and neutral surface charge adsorbed more serum proteins than the dextran-coated SPIONs, which resulted in higher blood circulation time for PVA-coated NPs than the dextran-coated ones. Highly abundant proteins such as serum albumin, serotransferrin, prothrombin, alpha-fetoprotein, and kininogen-1 were commonly found on both PVA- and dextran-coated SPIONs. By increasing the ionic strength, soft- and hard-corona proteins were observed on 3 types of PVA-SPIONs. However, the tightly bound proteins were observed only on negatively charged PVA-coated SPIONs after the strong protein elution.

Solution-based single molecule imaging of surface-immobilized conjugated polymers.

PubMed

Dalgarno, Paul A; Traina, Christopher A; Penedo, J Carlos; Bazan, Guillermo C; Samuel, Ifor D W

2013-05-15

The photophysical behavior of conjugated polymers used in modern optoelectronic devices is strongly influenced by their structural dynamics and conformational heterogeneity, both of which are dependent on solvent properties. Single molecule studies of these polymer systems embedded in a host matrix have proven to be very powerful to investigate the fundamental fluorescent properties. However, such studies lack the possibility of examining the relationship between conformational dynamics and photophysical response in solution, which is the phase from which films for devices are deposited. By developing a synthetic strategy to incorporate a biotin moiety as a surface attachment point at one end of a polyalkylthiophene, we immobilize it, enabling us to make the first single molecule fluorescence measurements of conjugated polymers for long periods of time in solution. We identify fluctuation patterns in the fluorescence signal that can be rationalized in terms of photobleaching and stochastic transitions to reversible dark states. Moreover, by using the advantages of solution-based imaging, we demonstrate that the addition of oxygen scavengers improves optical stability by significantly decreasing the photobleaching rates.

Dry particle coating of polymer particles for tailor-made product properties

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

Blümel, C., E-mail: karl-ernst.wirth@fau.de; Schmidt, J., E-mail: karl-ernst.wirth@fau.de; Dielesen, A., E-mail: karl-ernst.wirth@fau.de

2014-05-15

Disperse polymer powders with tailor-made particle properties are of increasing interest in industrial applications such as Selective Laser Beam Melting processes (SLM). This study focuses on dry particle coating processes to improve the conductivity of the insulating polymer powder in order to assemble conductive devices. Therefore PP particles were coated with Carbon Black nanoparticles in a dry particle coating process. This process was investigated in dependence of process time and mass fraction of Carbon Black. The conductivity of the functionalized powders was measured by impedance spectroscopy. It was found that there is a dependence of process time, respectively coating ratiomore » and conductivity. The powder shows higher conductivities with increasing number of guest particles per host particle surface area, i.e. there is a correlation between surface functionalization density and conductivity. The assembled composite particles open new possibilities for processing distinct polymers such as PP in SLM process. The fundamentals of the dry particle coating process of PP host particles with Carbon Black guest particles as well as the influence on the electrical conductivity will be discussed.« less

Structure-induced switching of interpolymer adhesion at a solid–polymer melt interface

DOE PAGES

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo; ...

2018-01-11

In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesionmore » testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chains and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.« less

Silicone-containing aqueous polymer dispersions with hybrid particle structure.

PubMed

Kozakiewicz, Janusz; Ofat, Izabela; Trzaskowska, Joanna

2015-09-01

In this paper the synthesis, characterization and application of silicone-containing aqueous polymer dispersions (APD) with hybrid particle structure are reviewed based on available literature data. Advantages of synthesis of dispersions with hybrid particle structure over blending of individual dispersions are pointed out. Three main processes leading to silicone-containing hybrid APD are identified and described in detail: (1) emulsion polymerization of organic unsaturated monomers in aqueous dispersions of silicone polymers or copolymers, (2) emulsion copolymerization of unsaturated organic monomers with alkoxysilanes or polysiloxanes with unsaturated functionality and (3) emulsion polymerization of alkoxysilanes (in particular with unsaturated functionality) and/or cyclic siloxanes in organic polymer dispersions. The effect of various factors on the properties of such hybrid APD and films as well as on hybrid particles composition and morphology is presented. It is shown that core-shell morphology where silicones constitute either the core or the shell is predominant in hybrid particles. Main applications of silicone-containing hybrid APD and related hybrid particles are reviewed including (1) coatings which show specific surface properties such as enhanced water repellency or antisoiling or antigraffiti properties due to migration of silicone to the surface, and (2) impact modifiers for thermoplastics and thermosets. Other processes in which silicone-containing particles with hybrid structure can be obtained (miniemulsion polymerization, polymerization in non-aqueous media, hybridization of organic polymer and polysiloxane, emulsion polymerization of silicone monomers in silicone polymer dispersions and physical methods) are also discussed. Prospects for further developments in the area of silicone-containing hybrid APD and related hybrid particles are presented. Copyright © 2015. Published by Elsevier B.V.

Self-healing polymers and composites based on thermal activation

NASA Astrophysics Data System (ADS)

Wang, Ying; Bolanos, Ed; Wudl, Fred; Hahn, Thomas; Kwok, Nathan

2007-04-01

Structural polymer composites are susceptible to premature failure in the form of microcracks in the matrix. Although benign initially when they form, these matrix cracks tend to coalesce and lead in service to critical damage modes such as ply delamination. The matrix cracks are difficult to detect and almost impossible to repair because they form inside the composite laminate. Therefore, polymers with self-healing capability would provide a promising potential to minimize maintenance costs while extending the service lifetime of composite structures. In this paper we report on a group of polymers and their composites which exhibit mendable property upon heating. The failure and healing mechanisms of the polymers involve Diels-Alder (DA) and retro-Diels-Alder (RDA) reactions on the polymer back-bone chain, which are thermally reversible reactions requiring no catalyst. The polymers exhibited good healing property in bulk form. Composite panels were prepared by sandwiching the monomers between carbon fiber fabric layers and cured in autoclave. Microcracks were induced on the resin-rich surface of composite with Instron machine at room temperature by holding at 1% strain for 1 min. The healing ability of the composite was also demonstrated by the disappearance of microcracks after heating. In addition to the self-healing ability, the polymers and composites also exhibited shape memory property. These unique properties may provide the material multi-functional applications. Resistance heating of traditional composites and its applicability in self-healing composites is also studied to lay groundwork for a fully integrated self-healing composite.

Cross-Linking Cellulosic Fibers with Photoreactive Polymers: Visualization with Confocal Raman and Fluorescence Microscopy.

PubMed

Janko, Marek; Jocher, Michael; Boehm, Alexander; Babel, Laura; Bump, Steven; Biesalski, Markus; Meckel, Tobias; Stark, Robert W

2015-07-13

The properties of paper sheets can be tuned by adjusting the surface or bulk chemistry using functional polymers that are applied during (online) or after (offline) papermaking processes. In particular, polymers are widely used to enhance the mechanical strength of the wet state of paper sheets. However, the mechanical strength depends not only on the chemical nature of the polymeric additives but also on the distribution of the polymer on and in the lignocellulosic paper. Here, we analyze the photochemical attachment and distribution of hydrophilic polydimethylacrylamide-co-methacrylate-benzophenone P(DMAA-co-MABP) copolymers with defined amounts of photoreactive benzophenone moieties in model paper sheets. Raman microscopy was used for the unambiguous identification of P(DMAA-co-MABP) and cellulose specific bands and thus the copolymer distribution within the cellulose matrix. Two-dimensional Raman spectral maps at the intersections of overlapping cellulose fibers document that the macromolecules only partially surround the cellulose fibers, favor to attach to the fiber surface, and connect the cellulose fibers at crossings. Moreover, the copolymer appears to accumulate preferentially in holes, vacancies, and dips on the cellulose fiber surface. Correlative brightfield, Raman, and confocal laser scanning microscopy finally reveal a reticular three-dimensional distribution of the polymer and show that the polymer is predominately deposited in regions of high capillarity (i.e., in proximity to fine cellulose fibrils). These data provide deeper insights into the effects of paper functionalization with a copolymer and aid in understanding how these agents ultimately influence the local and overall properties of paper.

Applications of functional polymer brushes for nanoparticle uptake and prevention of protein adsorption

NASA Astrophysics Data System (ADS)

Arifuzzaman, Shafi M.

The central theme of this Ph.D. dissertation is to develop novel multifunctional polymer coatings for understanding partition of proteins and nanoparticles on polymers grafted to flat surfaces (so-called brushes). Systematic investigation of the adsorption phenomena is accomplished by utilizing surface-anchored assemblies comprising grafted polymers with variation in physical properties (i.e., length or/and grafting density) and chemical functionality. The chemical composition of the brush is tailored by either "chemical coloring" of a parent homopolymer brush with selective chemical moieties or by sequential growth of two chemically dissimilar polymer blocks. We present preparation of two types of tailor-made, surface-grafted copolymers: (1) those composed of hydrophilic and hydrophobic blocks (so-called amphiphilic polymer brushes), and (2) those comprising of anionic and cationic polymer segments (so-called polyampholyte brushes). We describe the organization of functionality in the grafted polymer brushes and the partitioning of proteins and nanoparticles using a battery of complementary analytical probes. Specifically, we address how varying the molecular weight, grafting density, and chemical composition of the brush affects adsorbtion and desorbtion of model proteins and gold nanoparticles. Our observations indicate densely-populated responsive amphiphilic polymers are very efficient in suppressing protein adsorption. In addition, we have established that the length of poly(ethylene glycol) spacers attached to a parent homopolymer brush is a key factor governing uptake of gold nanoparticles. Both grafting density and molecular weight of the coating are important in controlling the kinetics and thermodynamics of protein adsorption on surfaces. Our findings and methodologies can lead to the development of next generation environmentally friendly antifouling surfaces and will find application in medical devices, antifouling coatings and anti reflection finishes.

Use of Atomic Oxygen for Increased Water Contact Angles of Various Polymers for Biomedical Applications

NASA Technical Reports Server (NTRS)

Beger, Lauren; Roberts, Lily; deGroh, Kim; Banks, Bruce

2007-01-01

In the low Earth orbit (LEO) space environment, spacecraft surfaces can be altered during atomic oxygen exposure through oxidation and erosion. There can be terrestrial benefits of such interactions, such as the modification of hydrophobic or hydrophilic properties of polymers due to chemical modification and texturing. Such modification of the surface may be useful for biomedical applications. For example, atomic oxygen texturing may increase the hydrophilicity of polymers, such as chlorotrifluoroethylene (Aclar), thus allowing increased adhesion and spreading of cells on textured Petri dishes. The purpose of this study was to determine the effect of atomic oxygen exposure on the hydrophilicity of nine different polymers. To determine whether hydrophilicity remains static after atomic oxygen exposure or changes with exposure, the contact angles between the polymer and a water droplet placed on the polymer s surface were measured. The polymers were exposed to atomic oxygen in a radio frequency (RF) plasma asher. Atomic oxygen plasma treatment was found to significantly alter the hydrophilicity of non-fluorinated polymers. Significant decreases in the water contact angle occurred with atomic oxygen exposure. Fluorinated polymers were found to be less sensitive to changes in hydrophilicity for equivalent atomic oxygen exposures, and two of the fluorinated polymers became more hydrophobic. The majority of change in water contact angle of the non-fluorinated polymers was found to occur with very low fluence exposures, indicating potential cell culturing benefit with short treatment time.

Surface electroluminescence phenomena correlated with trapping parameters of insulating polymers

NASA Astrophysics Data System (ADS)

Zhang, Guan-Jun; Yang, Kai; Dong, Ming; Zhao, Wen-Bin; Yan, Zhang

2007-12-01

Electroluminescence (EL) phenomena are closely linked to the space charge and degradation in insulating polymers, and dominated by the luminescence and trap centers. EL emission has been promising in defining the onset of electrical aging and in the investigation of dissipation mechanisms. Generally, polymeric degradation reveals the increment of the density of luminescence and trap centers, so a fundamental study is proposed to correlate the EL emission of insulating polymers and their trapping parameters. A sensitive photon counting system is constructed to detect the weak EL. The time- and phase-resolved EL characteristics from different polymers (LDPE, PP and PTFE) are investigated with a planar electrode configuration under stepped ac voltage in vacuum. In succession, each sample is charged with exposing to multi-needle corona discharge, and then its surface potential decay is continuously recorded at a constant temperature. Based on the isothermal relaxation current theory, the energy level and density of both electron and hole trap distribution in the surface layer of each polymer is obtained. It is preliminarily concluded that EL phenomena are strongly affected by the trap properties, and for different polymers, its EL intensity is in direct contrast to its surface trap density, and this can be qualitatively explained by the trapping and detrapping sequence of charge carriers in trap centers with different energy level.

PPV-Based Conjugated Polymer Nanoparticles as a Versatile Bioimaging Probe: A Closer Look at the Inherent Optical Properties and Nanoparticle-Cell Interactions.

PubMed

Peters, Martijn; Zaquen, Neomy; D'Olieslaeger, Lien; Bové, Hannelore; Vanderzande, Dirk; Hellings, Niels; Junkers, Thomas; Ethirajan, Anitha

2016-08-08

Conjugated polymers have attracted significant interest in the bioimaging field due to their excellent optical properties and biocompatibility. Tailor-made poly(p-phenylenevinylene) (PPV) conjugated polymer nanoparticles (NPs) are in here described. Two different nanoparticle systems using poly[2-methoxy-5-(3',7'-dimethoxyoctyloxy)-1,4-phenylenevinylene] (MDMO-PPV) and a functional statistical copolymer 2-(5'-methoxycarbonylpentyloxy)-5-methoxy-1,4-phenylenevinylene (CPM-MDMO-PPV), containing ester groups on the alkoxy side chains, were synthesized by combining miniemulsion and solvent evaporation processes. The hydrolysis of ester groups into carboxylic acid groups on the CPM-MDMO-PPV NPs surface allows for biomolecule conjugation. The NPs exhibited excellent optical properties with a high fluorescent brightness and photostability. The NPs were in vitro tested as potential fluorescent nanoprobes for studying cell populations within the central nervous system. The cell studies demonstrated biocompatibility and surface charge dependent cellular uptake of the NPs. This study highlights that PPV-derivative based particles are a promising bioimaging probe and can cater potential applications in the field of nanomedicine.

Characterization of the surface properties of epoxy-type models used for multiphase flow studies in fractured media and creation of a new model

NASA Astrophysics Data System (ADS)

Bergslien, Elisa; Fountain, John; Giese, Rossman

2004-05-01

Epoxy models have been used as analogs for fractured rock surfaces in many laboratory investigations of multiphase flow processes. However, there is no agreement on how well or poorly such an analog replicates the surface chemistry of geologic materials, nor is there a satisfactory analysis of the surface properties of epoxy. This paper addresses the issue of accurately characterizing the surface chemistry of a typical epoxy used in laboratory multiphase flow studies and comparing that surface to a polystyrene surface and a radio frequency glow discharge treated polystyrene surface. Surface properties were determined using direct contact angle measurements of polar and apolar liquids on flat test samples. The epoxy was determined to have surface properties as follows: γ = 62.3, γLW = 39, γAB = 23.3, γ⊕ = 0, and γ? = 23.3 mJ/m2, where γ is the total surface tension of the solid, γLW is the Lifshitz-van der Waals (LW) surface tension component, γAB is the Lewis acid base (AB) surface tension component, γ? is the electron-donor (negative) parameter, and γ⊕ is the electron-acceptor (positive) parameter. Values of γ? < 27.9 mJ/m2 indicate a hydrophobic surface, which means that epoxy is not a good analog for most geologic materials. This study also explores the use of radio frequency glow discharge plasma to add hydroxyl functionality to polymer surfaces producing a material with alterable surface properties and the same optical and casting properties as epoxy. Using this method, the degree of alteration of the surface chemistry of polymer fracture models can be controlled, allowing the creation of models with a variety of different wettabilities. The resultant models were found to be durable, long lasting, and a potentially very useful alternative to the more typical epoxy models.

Novel alkyd-type coating resins produced using cationic polymerization

DOE PAGES

Chisholm, Bret J.; Kalita, Harjyoti; Alam, Samim; ...

2015-05-06

Novel, partially bio-based poly(vinyl ether) copolymers derived from soybean oil and cyclohexyl vinyl ether (CHVE) were produced by cationic polymerization and investigated for application as alkyd-type surface coatings. Compared to conventional alkyd resins, which are produced by high temperature melt condensation polymerization, the poly(v9nyl ether)s provide several advantages. These advantages include milder, more energy efficient polymer synthesis, elimination of issues associated with gelation during polymer synthesis, production of polymers with well-defined composition and relatively narrow molecular weight distribution, and elimination of film formation and physical property issues associated with entrained monomers, dimers, trimers, etc. The results of the studied showedmore » that the thermal, mechanical, and physical properties of the coatings produced from these novel polymers varied considerably as a function of polymer composition and cure temperature. Overall, the results suggest a good potential for these novel copolymers to be used for coatings cured by autoxidation.« less

Multifunctional polymer nano-composite based superhydrophobic surface

NASA Astrophysics Data System (ADS)

Maitra, Tanmoy; Asthana, Ashish; Buchel, Robert; Tiwari, Manish K.; Poulikakos, Dimos

2014-11-01

Superhydrophobic surfaces become desirable in plethora of applications in engineering fields, automobile industry, construction industries to name a few. Typical fabrication of superhydrophobic surface consists of two steps: first is to create rough morphology on the substrate of interest, followed by coating of low energy molecules. However, typical exception of the above fabrication technique would be direct coating of functional polymer nanocomposites on substrate where superhydrophobicity is needed. Also in this case, the use of different nanoparticles in the polymer matrix can be exploited to impart multi-functional properties to the superhydrophobic coatings. Herein, different carbon nanoparticles like graphene nanoplatelets (GNP), carbon nanotubes (CNT) and carbon black (CB) are used in fluropolymer matrix to prepare superhydrophobic coatings. The multi-functional properties of coatings are enhanced by combining two different carbon fillers in the matrix. The aforementioned superhydrophobic coatings have shown high electrical conductivity and excellent droplet meniscus impalement resistance. Simultaneous superhydrophobic and oleophillic character of the above coating is used to separate mineral oil and water through filtration of their mixture. Swiss National Science Foundation (SNF) Grant 200021_135479.

Biomaterials functionalization using a novel peptide that selectively binds to a conducting polymer

NASA Astrophysics Data System (ADS)

Sanghvi, Archit B.; Miller, Kiley P.-H.; Belcher, Angela M.; Schmidt, Christine E.

2005-06-01

The goal in biomaterial surface modification is to retain a material's bulk properties while modifying only its surface to possess desired recognition and specificity. Here we develop a unique strategy for surface functionalization of an electrically conductive polymer, chlorine-doped polypyrrole (PPyCl), which has been widely researched for various electronic and biomedical applications. An M13 bacteriophage library was used to screen 109 different 12-mer peptide inserts against PPyCl. A binding phage (ϕT59) was isolated, and its binding stability and specificity to PPyCl was assessed using fluorescence microscopy and titer count analysis. The relative binding strength and mechanism of the corresponding 12-mer peptide and its variants was studied using atomic force microscopy and fluorescamine assays. Further, the T59 peptide was joined to a cell adhesive sequence and used to promote cell attachment on PPyCl. This strategy can be extended to immobilize a variety of molecules to PPyCl for numerous applications. In addition, phage display can be applied to other polymers to develop bioactive materials without altering their bulk properties.

Protection of Conductive and Non-conductive Advanced Polymer-based Paints from Highly Aggressive Oxidative Environments

NASA Technical Reports Server (NTRS)

Gudimenko, Y.; Ng, R.; Iskanderova, Z.; Kleiman, J.; Grigorevsky, A.; Kiseleva, L.; Finckenor, M.; Edwards, D.

2005-01-01

Research has been continued to further improve the space durability of conductive and non-conductive polymer-based paints and of conductive thermal control paints for space applications. Efforts have been made to enhance the space durability and stability of functional Characteristics in ground-based space environment imitating conditions, using specially developed surface modification treatment. The results of surface modification of new conductive paints, including the ground-based testing in aggressive oxidative environments, such as atomic oxygen/UV and oxygen plasma, and performance evaluation are presented. Functional properties and performance characteristics, such as thermal optical properties (differential solar absorptance and thermal emittance representing the thermal optical performance of thermal control paints) and surface resistivity characteristics of pristine, surface modified, and tested materials were verified. Extensive surface analysis studies have been performed using complementary surface analyses including SEM/EDS and XPS. Test results revealed that the successfully treated materials exhibit reduced mass loss and no surface morphology change, thus indicating good protection from the severe oxidative environment. It was demonstrated that the developed surface modification treatment could be applied successfully to charge dissipative and conductive paints.

Clay-based polymer nanocomposites: research and commercial development.

PubMed

Zeng, Q H; Yu, A B; Lu, G Q; Paul, D R

2005-10-01

This paper reviews the recent research and development of clay-based polymer nanocomposites. Clay minerals, due to their unique layered structure, rich intercalation chemistry and availability at low cost, are promising nanoparticle reinforcements for polymers to manufacture low-cost, lightweight and high performance nanocomposites. We introduce briefly the structure, properties and surface modification of clay minerals, followed by the processing and characterization techniques of polymer nanocomposites. The enhanced and novel properties of such nanocomposites are then discussed, including mechanical, thermal, barrier, electrical conductivity, biodegradability among others. In addition, their available commercial and potential applications in automotive, packaging, coating and pigment, electrical materials, and in particular biomedical fields are highlighted. Finally, the challenges for the future are discussed in terms of processing, characterization and the mechanisms governing the behaviour of these advanced materials.

The sorption properties of polymers with molecular imprints of 2,4-dichlorophenoxyacetic acid synthesized by various methods

NASA Astrophysics Data System (ADS)

Dmitrienko, S. G.; Popov, S. A.; Chumichkina, Yu. A.; Zolotov, Yu. A.

2011-03-01

New sorbents, polymers with molecular imprints of 2,4-dichlorophenoxyacetic acid (2,4-D), were prepared on the basis of acrylamide. The sorbents were synthesized by thermal polymerization methods with and without the use of ultrasound, photopolymerization, and suspension polymerization. The specific surface area of the products was estimated and their sorption properties were studied. Polymers with molecular imprints prepared by thermal polymerization with the use of ultrasound and by suspension polymerization showed the best ability to repeatedly bind 2,4-D. The selectivity of polymers was estimated for the example of structurally related compounds. It was shown that the method of synthesis decisively influenced not only the ability of sorbents to repeatedly bind 2,4-D but also their selectivity.

Polymer surface functionalities that control human embryoid body cell adhesion revealed by high throughput surface characterization of combinatorial material microarrays

PubMed Central

Yang, Jing; Mei, Ying; Hook, Andrew L.; Taylor, Michael; Urquhart, Andrew J.; Bogatyrev, Said R.; Langer, Robert; Anderson, Daniel G.; Davies, Martyn C.; Alexander, Morgan R.

2010-01-01

High throughput materials discovery using combinatorial polymer microarrays to screen for new biomaterials with new and improved function is established as a powerful strategy. Here we combine this screening approach with high throughput surface characterisation (HT-SC) to identify surface structure-function relationships. We explore how this combination can help to identify surface chemical moieties that control protein adsorption and subsequent cellular response. The adhesion of human embryoid body (hEB) cells to a large number (496) of different acrylate polymers synthesized in a microarray format is screened using a high throughput procedure. To determine the role of the polymer surface properties on hEB cell adhesion, detailed HT-SC of these acrylate polymers is carried out using time of flight secondary ion mass spectrometry (ToF SIMS), x-ray photoelectron spectroscopy (XPS), pico litre drop sessile water contact angle (WCA) measurement and atomic force microscopy (AFM). A structure-function relationship is identified between the ToF SIMS analysis of the surface chemistry after a fibronectin (Fn) pre-conditioning step and the cell adhesion to each spot using the multivariate analysis technique partial least squares (PLS) regression. Secondary ions indicative of the adsorbed Fn correlate with increased cell adhesion whereas glycol and other functionalities from the polymers are identified that reduce cell adhesion. Furthermore, a strong relationship between the ToF SIMS spectra of bare polymers and the cell adhesion to each spot is identified using PLS regression. This identifies a role for both the surface chemistry of the bare polymer and the pre-adsorbed Fn, as-represented in the ToF SIMS spectra, in controlling cellular adhesion. In contrast, no relationship is found between cell adhesion and wettability, surface roughness, elemental or functional surface composition. The correlation between ToF SIMS data of the surfaces and the cell adhesion demonstrates the ability of identifying surface moieties that control protein adsorption and subsequent cell adhesion using ToF SIMS and multivariate analysis. PMID:20832108

Computational modeling of in vitro biological responses on polymethacrylate surfaces

PubMed Central

Ghosh, Jayeeta; Lewitus, Dan Y; Chandra, Prafulla; Joy, Abraham; Bushman, Jared; Knight, Doyle; Kohn, Joachim

2011-01-01

The objective of this research was to examine the capabilities of QSPR (Quantitative Structure Property Relationship) modeling to predict specific biological responses (fibrinogen adsorption, cell attachment and cell proliferation index) on thin films of different polymethacrylates. Using 33 commercially available monomers it is theoretically possible to construct a library of over 40,000 distinct polymer compositions. A subset of these polymers were synthesized and solvent cast surfaces were prepared in 96 well plates for the measurement of fibrinogen adsorption. NIH 3T3 cell attachment and proliferation index were measured on spin coated thin films of these polymers. Based on the experimental results of these polymers, separate models were built for homo-, co-, and terpolymers in the library with good correlation between experiment and predicted values. The ability to predict biological responses by simple QSPR models for large numbers of polymers has important implications in designing biomaterials for specific biological or medical applications. PMID:21779132

Preparation and Characterization of Polyimide Nanocomposites

NASA Technical Reports Server (NTRS)

Orwoll, Robert A.

2002-01-01

Many properties of polymeric materials can be enhanced by dispersing small quantities of clay nanocomposites throughout the polymer. Among the enhancements are increases in modulus and resistance to erosion by atomic oxygen and reductions in thermal expansivity, gas permeability, and flammability. To achieve the full extent of enhancement with these polymer-clay nanocomposites, the clay nanoparticles, which have thicknesses of only one-to-several nanometers and lengths and widths of hundreds of nanometers to micrometers, must be exfoliated one from another and then individually dispersed throughout the polymer. This dispersion is achieved only after alkali metal cations (usually Na(+)) that reside on the surfaces of the nanoparticles have been replaced by organocations (typically a quaternary amine cation). This renders the surface of the nanoparticle a more hospitable interface for the organic polymer matrix. Following the cation exchange, the organic clay is either mixed directly into the polymer or is dispersed in monomer which is later polymerized around the nanoparticle.

Enhancement of mechanical properties of polymers by thin flake addition and apparatus for producing such thin flakes

DOEpatents

Bunnell, Sr., Lee R.

1991-01-01

Compositions in accordance with the invention comprise a polymer and flake reinforcing material distributed throughout the polymer in an effective amount to structurally reinforce the polymer. Individual flakes of the flake material (a) are less than or equal to 1,000 Angstroms in thickness, (b) have an aspect ratio greater than or equal to 100, and (c) are preferably significantly randomly oriented throughout the polymer. A novel apparatus for shear grinding a platy solid material into such individual flakes comprises a cylindrical shearing drum and a shear grinder received therein. The shearing drum has a longitudinal axis and an internal surface formed about a first predetermined radius of curvature. The cylindrical drum is supported for rotation about its longitudinal axis. The shear grinder has an external surface formed about a second predetermined radius of curvature. The second radius of curvature is slightly less than the first radius of curvature.

Computational approach to the study of morphological properties of polymer/fullerene blends in photovoltaics

NASA Astrophysics Data System (ADS)

Gaitho, Francis M.; Mola, Genene T.; Pellicane, Giuseppe

2018-02-01

Organic solar cells have the ability to transform solar energy efficiently and have a promising energy balance. Producing these cells is economical and makes use of methods of printing using inks built on solvents that are well-matched with a variety of cheap materials like flexible plastic or paper. The primary materials used to manufacture organic solar cells include carbon-based semiconductors, which are good light absorbers and efficient charge generators. In this article, we review previous research of interest based on morphology of polymer blends used in bulk heterojunction (BHJ) solar cells and introduce their basic principles. We further review computational models used in the analysis of surface behavior of polymer blends in BHJ as well as the trends in the field of polymer surface science as applied to BHJ photovoltaics. We also give in brief, the opportunities and challenges in the area of polymer blends on BHJ organic solar cells.

Adsorption of polyethyleneimine and polymethacrylic acid onto synthesized hematite.

PubMed

Chibowski, S; Patkowski, J; Grzadka, E

2009-01-01

An influence of different functional groups of polymer, its molecular weight, polydispersity ratio (M(w)/M(n)) and presence of impurities on its adsorption in different pH values (3, 6 and 9) onto synthesized hematite (Fe(2)O(3)) was measured. A structure of adsorbed macromolecules of PMA and PEI was obtained according to S-F theory. Two polymers were used: polymethacrylic acid (PMA) of 6500 and 75,100 molecular weight as well as polyethyleneimine (PEI) 25,000 commercial and fractionated. Electrokinetic properties of the interface oxide-polymer solution (surface charge density and zeta potential) were also measured as well as adsorption layer thicknesses (with use of viscosimetric measurements). Obtained data show, that all above-mentioned factors do influence not only the adsorption process itself but also a surface charge, zeta potential and structure of adsorbed polymer layers on polymer/hematite interface.

Polymer-metal hybrid transparent electrodes for flexible electronics

NASA Astrophysics Data System (ADS)

Kang, Hongkyu; Jung, Suhyun; Jeong, Soyeong; Kim, Geunjin; Lee, Kwanghee

2015-03-01

Despite nearly two decades of research, the absence of ideal flexible and transparent electrodes has been the largest obstacle in realizing flexible and printable electronics for future technologies. Here we report the fabrication of ‘polymer-metal hybrid electrodes’ with high-performance properties, including a bending radius <1 mm, a visible-range transmittance>95% and a sheet resistance <10 Ω sq-1. These features arise from a surface modification of the plastic substrates using an amine-containing nonconjugated polyelectrolyte, which provides ideal metal-nucleation sites with a surface-density on the atomic scale, in combination with the successive deposition of a facile anti-reflective coating using a conducting polymer. The hybrid electrodes are fully functional as universal electrodes for high-end flexible electronic applications, such as polymer solar cells that exhibit a high power conversion efficiency of 10% and polymer light-emitting diodes that can outperform those based on transparent conducting oxides.

Polymer-metal hybrid transparent electrodes for flexible electronics

PubMed Central

Kang, Hongkyu; Jung, Suhyun; Jeong, Soyeong; Kim, Geunjin; Lee, Kwanghee

2015-01-01

Despite nearly two decades of research, the absence of ideal flexible and transparent electrodes has been the largest obstacle in realizing flexible and printable electronics for future technologies. Here we report the fabrication of ‘polymer-metal hybrid electrodes’ with high-performance properties, including a bending radius <1 mm, a visible-range transmittance>95% and a sheet resistance <10 Ω sq−1. These features arise from a surface modification of the plastic substrates using an amine-containing nonconjugated polyelectrolyte, which provides ideal metal-nucleation sites with a surface-density on the atomic scale, in combination with the successive deposition of a facile anti-reflective coating using a conducting polymer. The hybrid electrodes are fully functional as universal electrodes for high-end flexible electronic applications, such as polymer solar cells that exhibit a high power conversion efficiency of 10% and polymer light-emitting diodes that can outperform those based on transparent conducting oxides. PMID:25790133

Programmable and electrically controllable light scattering from surface-polymer stabilized liquid crystals.

PubMed

Bédard-Arcand, Jean-Philippe; Galstian, Tigran

2012-08-01

We report the creation and study of a polarization independent light scattering material system based on surface-polymer stabilized liquid crystals. Originally isotropic cell substrates with thin nonpolymerized reactive mesogen layers are used for the alignment of pure nonreactive nematic liquid crystals. The partial interdiffusion of the two materials followed by the application of orienting external electric and magnetic fields and the photo polymerization of the reactive mesogen allow us the control of electro-optic scattering properties of obtained cells.

Derivatizing weak polyelectrolytes--solution properties, self-aggregation, and association with anionic surfaces of hydrophobically modified poly(ethylene imine).

PubMed

Griffiths, Peter C; Paul, Alison; Fallis, Ian A; Wellappili, Champa; Murphy, Damien M; Jenkins, Robert; Waters, Sarah J; Nilmini, Renuka; Heenan, Richard K; King, Stephen M

2007-10-15

The physical properties of weak polyelectrolytes may be tailored via hydrophobic modification to exhibit useful properties under appropriate pH and ionic strength conditions as a consequence of the often inherently competing effects of electrostatics and hydrophobicity. Pulsed-gradient spin-echo NMR (PGSE-NMR), electron paramagnetic resonance (EPR), small-angle neutron scattering (SANS) surface tension, fluorescence, and pH titration have been used to examine the solution conformation and aggregation behavior of a series of hydrophobically modified hyperbranched poly(ethylene imine) (PEI) polymers in aqueous solution, and their interaction with sodium dodecylsulfate (SDS). PGSE-NMR gave a particularly insightful picture of the apparent molecular weight distribution. The presence of the hydrophobes led to a lower effective charge on the polymer at any given pH, compared to the (parent) nonmodified samples. Analysis of the SANS data showed that the propensity to form highly elliptical or rod-like aggregates at higher pHs, reflecting both the changes in protonation behavior induced by the hydrophobic modification and an hydrophobic interaction, but that these structures were disrupted with decreasing pH (increasing charge). The parent samples were not surface active yet the hydrophobically modified samples show pronounced surface activity and the presence of small hydrophobic domains. The surface activity increased with an increase in the degree of modification. On addition of SDS, the onset of the formation of polymer/surfactant complexes was insensitive to the degree of modification with the resultant PEI/SDS complexes resembling the size and shape of simple SDS micelles. Indeed, the presence of the SDS effectively nullifies the effects of the hydrophobe. Hydrophobic modification is therefore a viable option to tailor pH dependent properties, whose effects may be removed by the presence of surfactant.

Bioactivity of Hybrid Polymeric Magnetic Nanoparticles and Their Applications in Drug Delivery.

PubMed

Mohammed, Leena; Ragab, Doaa; Gomaa, Hassan

2016-01-01

Engineered magnetic nanoparticles (MNPs) possess unique properties and hold great potential in biomedicine and clinical applications. With their magnetic properties and their ability to work at cellular and molecular level, MNP have been applied both in-vitro and in-vivo in targeted drug delivery and imaging. Focusing on Iron Oxide Superparamagnetic nanoparticles (SPIONs), this paper elaborates on the recent advances in development of hybrid polymeric-magnetic nanoparticles. Their main applications in drug delivery include Chemotherapeutics, Hyperthermia treatment, Radio-therapeutics, Gene delivary, and Biotheraputics. Physiochemical properties such as size, shape, surface and magnetic properties are key factors in determining their behavior. Additionally tailoring SPIONs surface is often vital for desired cell targetting and improved efficiency. Polymer coating is specifically reviewed with brief discussion of SPIONs administration routes. Commonly used drug release models for describing release mechanisms and the nanotoxicity aspects are also discussed. This review focus on superparamagnetic nanoparticles coated with different types of polymers starting with the key physiochemical features that dominate their behavior. The importance of surface modification is addressed. Subsequently, the major classes of polymer modified iron oxide nanoparticles is demonstrated according to their clinical use and application. Clinically approved nanoparticles are then addressed and the different routes of administration are mentioned. Lastly, mathematical models of drug release profile of the common used nanoparticles are addressed. MNPs emerging in recent medicine are remarkable for both imaging and therapeutics, particularly, as drug carriers for their great potential in targeted delivery and cancer treatment. Targeting ability and biocompatibility can be improved though surface coating which provides a mean to alter the surface features including physical characteristics and chemical functionality. The use of biocompatible polymers can prevent aggregation, increase colloidal stability, evades nanoparticles uptake by RES, and can provide a surface for conjugation of targeting ligands such as peptide and biomolecules with high affinity to target cells. Great efforts to bring MNPs from lab testing stage to clinic are needed to understand their physicochemical properties and how they behave in vivo, which resulted in few of them to exist in the market today. Although magnetic nanoparticles have not yet fully reached their optimal safety and efficiency due to the challenges they face in vivo, their shortcomings can be overcome through improvement of magnetictargeted carrier by pre-clinical trials and continuous studies.

Biomimetic nanocoatings with exceptional mechanical, barrier, and flame-retardant properties from large-scale one-step coassembly

PubMed Central

Ding, Fuchuan; Liu, Jingjing; Zeng, Songshan; Xia, Yan; Wells, Kacie M.; Nieh, Mu-Ping; Sun, Luyi

2017-01-01

Large-scale biomimetic organic/inorganic hybrid nanocoatings with a nacre-like microstructure were prepared via a facile coassembly process. Different from conventional polymer nanocomposites, these nanocoatings contain a high concentration of nanosheets, which can be well aligned along the substrate surface. Moreover, the nanosheets and polymer matrix can be chemically co–cross-linked. As a result, the nanocoatings exhibit exceptional mechanical properties (high stiffness and strength), barrier properties (to both oxygen and water vapor), and flame retardancy, but they are also highly transparent (maintaining more than 85% of their original transmittance to visible light). The nanocoatings can be applied to various substrates and regular or irregular surfaces (for example, films and foams). Because of their excellent performance and high versatility, these nanocoatings are expected to find widespread application. PMID:28776038

Origin of organic matter in the early solar system. VII - The organic polymer in carbonaceous chondrites

NASA Technical Reports Server (NTRS)

Hayatsu, R.; Matsuoka, S.; Anders, E.; Scott, R. G.; Studier, M. H.

1977-01-01

Degradation techniques, including pyrolysis, depolymerization, and oxidation, were used to study the insoluble polymer from the Murchison C2 chondrite. Oxidation with Cr2O7(2-) or O2/UV led to the identification of 15 aromatic ring systems. Of 11 aliphatic acids identified, three dicarboxylic acids presumably came from hydroaromatic portions of the polymer, whereas eight monocarboxylic acids probably derive from bridging groups or ring substituents. Depolymerization with CF3COO4 yielded some of the same ring systems, as well as alkanes (C1 through C8) and alkenes (C2 through C8), alkyl (C1 through C5) benzenes and naphthalenes, and methyl- or dimethyl -indene, -indane, -phenol, -pyrrole, and -pyridine. All these compounds were detected below 200 C, and are therefore probably indigenous constituents. The properties of the meteoritic polymer were compared with the properties of a synthetic polymer produced by the Fischer-Tropsch reaction. It is suggested that the meteoritic polymer was also produced by surface catalysis.

Optical and Thermo-optical Properties of Polyimide-Single-Walled Carbon Nanotube Films: Experimental Results and Empirical Equations

NASA Technical Reports Server (NTRS)

Smith, Joseph G., Jr.; Connell, John W.; Watson, Kent A.; Danehy, Paul M.

2005-01-01

The incorporation of single-walled carbon nanotubes (SWNTs) into the bulk of space environmentally durable polymers at loading levels greater than or equal to 0.05 wt % has afforded thin films with surface and volume resistivities sufficient for electrostatic charge mitigation. However, the optical transparency at 500 nm decreased and the thermo-optical properties (solar absorptivity and thermal emissivity) increased with increaed SWNT loading. These properties were also dependent on film thickness. The absorbance characteristics of the films as a function of SWNT loading and film thickness were measured and determined to follow the classical Beer-Lambert law. Based on these results, an empirical relationship was derived and molar absorptivities determined for both the SWNTs and polymer matrix to provide a predictive approximation of these properties. The molar absorptivity determined for SWNTs dispersed in the polymer was comparable to reported solution determined values for HiPco SWNTs.

Various nanoparticle morphologies and surface properties of waterborne polyurethane controlled by water

PubMed Central

Zhou, Xing; Fang, Changqing; Lei, Wanqing; Du, Jie; Huang, Tingyi; Li, Yan; Cheng, Youliang

2016-01-01

Water plays important roles in organic reactions such as polyurethane synthesis, and the aqueous solution environment affects polymer morphology and other properties. This paper focuses on the morphology and surface properties of waterborne polyurethane resulting from the organic reaction in water involving different forms (solid and liquid), temperatures and aqueous solutions. We provide evidence from TEM observations that the appearance of polyurethane nanoparticles in aqueous solutions presents diverse forms, including imperfect spheres, perfect spheres, perfect and homogenous spheres and tubes. Based on the results on FTIR, GPC, AFM and XRD experiments, we suggest that the shape of the nanoparticles may be decided by the crimp degree (i.e., the degree of polyurethane chains intertangling in the water environment) and order degree, which are determined by the molecular weight (Mn) and hydrogen bonds. Meanwhile, solid water and high-temperature water can both reduce hard segments that gather on the polyurethane film surface to reduce hydrophilic groups and produce a soft surface. Our findings show that water may play key roles in aqueous polymer formation and bring order to molecular chains. PMID:27687001

Optical Spectroscopy of New Materials

NASA Technical Reports Server (NTRS)

White, Susan M.; Arnold, James O. (Technical Monitor)

1993-01-01

Composites are currently used for a rapidly expanding number of applications including aircraft structures, rocket nozzles, thermal protection of spacecraft, high performance ablative surfaces, sports equipment including skis, tennis rackets and bicycles, lightweight automobile components, cutting tools, and optical-grade mirrors. Composites are formed from two or more insoluble materials to produce a material with superior properties to either component. Composites range from dispersion-hardened alloys to advanced fiber-reinforced composites. UV/VIS and FTIR spectroscopy currently is used to evaluate the bonding between the matrix and the fibers, monitor the curing process of a polymer, measure surface contamination, characterize the interphase material, monitor anion transport in polymer phases, characterize the void formation (voids must be minimized because, like cracks in a bulk material, they lead to failure), characterize the surface of the fiber component, and measure the overall optical properties for energy balances.

Molecular Design of Antifouling Polymer Brushes Using Sequence-Specific Peptoids.

PubMed

Lau, King Hang Aaron; Sileika, Tadas S; Park, Sung Hyun; Sousa, Ana Maria Leal; Burch, Patrick; Szleifer, Igal; Messersmith, Phillip B

2015-01-07

Material systems that can be used to flexibly and precisely define the chemical nature and molecular arrangement of a surface would be invaluable for the control of complex biointerfacial interactions. For example, progress in antifouling polymer biointerfaces that prevent non-specific protein adsorption and cell attachment, which can significantly improve the performance of an array of biomedical and industrial applications, is hampered by a lack of chemical models to identify the molecular features conferring their properties. Poly(N-substituted glycine) "peptoids" are peptidomimetic polymers that can be conveniently synthesized with specific monomer sequences and chain lengths, and are presented as a versatile platform for investigating the molecular design of antifouling polymer brushes. Zwitterionic antifouling polymer brushes have captured significant recent attention, and a targeted library of zwitterionic peptoid brushes with a different charge densities, hydration, separations between charged groups, chain lengths, and grafted chain densities, is quantitatively evaluated for their antifouling properties through a range of protein adsorption and cell attachment assays. Specific zwitterionic brush designs were found to give rise to distinct but subtle differences in properties. The results also point to the dominant roles of the grafted chain density and chain length in determining the performance of antifouling polymer brushes.

Printable Top-Gate-Type Polymer Light-Emitting Transistors with Surfaces of Amorphous Fluoropolymer Insulators Modified by Vacuum Ultraviolet Light Treatment

NASA Astrophysics Data System (ADS)

Kajii, Hirotake; Terashima, Daiki; Kusumoto, Yusuke; Ikezoe, Ikuya; Ohmori, Yutaka

2013-04-01

We investigated the fabrication and electrical and optical properties of top-gate-type polymer light-emitting transistors with the surfaces of amorphous fluoropolymer insulators, CYTOP (Asahi Glass) modified by vacuum ultraviolet light (VUV) treatment. The surface energy of CYTOP, which has a good solution barrier property was increased by VUV irradiation, and the gate electrode was fabricated by solution processing on the CYTOP film using the Ag nano-ink. The influence of VUV irradiation on the optical properties of poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) films with various gate insulators was investigated to clarify the passivation effect of gate insulators. It was found that the poly(methyl methacrylate) (PMMA) film prevented the degradation of the F8BT layer under VUV irradiation because the PMMA film can absorb VUV. The solution-processed F8BT device with multilayer PMMA/CYTOP insulators utilizing a gate electrode fabricated using the Ag nano-ink exhibited both the ambipolar characteristics and yellow-green emission.

Tuning Surface Properties of Poly(methyl methacrylate) Film Using Poly(perfluoromethyl methacrylate)s with Short Perfluorinated Side Chains.

PubMed

Sohn, Eun-Ho; Ha, Jong-Wook; Lee, Soo-Bok; Park, In Jun

2016-09-27

To control the surface properties of a commonly used polymer, poly(methyl methacrylate) (PMMA), poly(perfluoromethyl methacrylate)s (PFMMAs) with short perfluorinated side groups (i.e., -CF3, -CF2CF3, -(CF3)2, -CF2CF2CF3) were used as blend components because of their good solubility in organic solvents, low surface energies, and high optical transmittance. The surface energies of the blend films of PFMMA with the -CF3 group and PMMA increased continuously with increasing PMMA contents from 17.6 to 26.0 mN/m, whereas those of the other polymer blend films remained at very low levels (10.2-12.6 mN/m), similar to those of pure PFMMAs, even when the blends contained 90 wt %PMMA. Surface morphology and composition measurements revealed that this result originated from the different blend structures, such as lateral and vertical phase separations. We expect that these PFMMAs will be useful in widening the applicable window of PMMA.

Modification of polyvinyl alcohol surface properties by ion implantation

NASA Astrophysics Data System (ADS)

Pukhova, I. V.; Kurzina, I. A.; Savkin, K. P.; Laput, O. A.; Oks, E. M.

2017-05-01

We describe our investigations of the surface physicochemical properties of polyvinyl alcohol modified by silver, argon and carbon ion implantation to doses of 1 × 1014, 1 × 1015 and 1 × 1016 ion/cm2 and energies of 20 keV (for C and Ar) and 40 keV (for Ag). Infrared spectroscopy (IRS) indicates that destructive processes accompanied by chemical bond (sbnd Cdbnd O) generation are induced by implantation, and X-ray photoelectron spectroscopy (XPS) analysis indicates that the implanted silver is in a metallic Ag3d state without stable chemical bond formation with polymer chains. Ion implantation is found to affect the surface energy: the polar component increases while the dispersion part decreases with increasing implantation dose. Surface roughness is greater after ion implantation and the hydrophobicity increases with increasing dose, for all ion species. We find that ion implantation of Ag, Ar and C leads to a reduction in the polymer microhardness by a factor of five, while the surface electrical resistivity declines modestly.

Immobilization of yeast cells with ionic hydrogel carriers by adhesion-multiplication.

PubMed

Zhaoxin, L; Fujimura, T

2000-12-01

The mixture of an ionic monomer, 2-acrylamido 2-methylpropanesulfonic acid (TBAS), and a series of poly(ethylene glycol) dimethacrylate (nG) monomers were copolymerized with 60Co gamma-rays, and the produced ionic hydrogel polymers were used for immobilization of yeast cells. The cells were adhered onto the surface of the hydrogel polymers and intruded into the interior of the polymers with growing. The immobilized yeast cells with these hydrogel polymers had higher ethanol productivity than that of free cells. The yield of ethanol with poly(TBAS-14G) carrier was the highest and increased by 3.5 times compared to the free cells. It was found that the ethanol yield increased with the increase of glycol number in poly(ethylene glycol) dimethacrylate. The state of the immobilized cells was observed with microscope, and it was also found that the difference in the ethanol productivity is mainly due to the difference in the internal structure and properties of polymer carrier, such as surface charge, hydrophilicity, and swelling ability of polymer carrier.

Tunable Electromagnetic Coupling in Plasmonic Nanostructures Mediated by Thermoresponsive Polymer Brushes.

PubMed

Nguyen, Mai; Kanaev, Andrei; Sun, Xiaonan; Lacaze, Emmanuelle; Lau-Truong, Stéphanie; Lamouri, Aazdine; Aubard, Jean; Felidj, Nordin; Mangeney, Claire

2015-11-24

A smart and highly SERS-active plasmonic platform was designed by coupling regular arrays of nanotriangles to colloidal gold nanorods via a thermoresponsive polymer spacer (poly(N-isopropylacrylamide), PNIPAM). The substrates were prepared by combining a top-down and a bottom-up approach based on nanosphere lithography, surface-initiated controlled radical polymerization, and colloidal assembly. This multistep strategy provided regular hexagonal arrays of nanotriangles functionalized by polymer brushes and colloidal gold nanorods, confined exclusively on the nanotriangle surface. Interestingly, one could finely tune the gold nanorod impregnation on the polymer-coated nanostructures by adjusting the polymer layer thickness, leading to highly coupled plasmonic systems for intense SERS signal. Moreover, the thermoresponsive properties of the PNIPAM brushes could be wisely handled in order to monitor the SERS activity of the nanostructures coupled via this polymer spacer. The coupled hybrid plasmonic nanostructures designed in this work are therefore very promising smart platforms for the sensitive detection of analytes by SERS.

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

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo

In this paper, we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: “flattened chains” which lie flat on the solid and are densely packed, and “loosely adsorbed polymer chains” which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesionmore » testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer–adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as “connector molecules”, bridging the free chains and substrate surface and improving the interfacial adhesion. Finally, these findings not only shed light on the structure–property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.« less

Adjustment of surface chemical and physical properties with functionalized polymers to control cell adhesion

NASA Astrophysics Data System (ADS)

Zhou, Zhaoli

Cell-surface interaction is crucial in many cellular functions such as movement, growth, differentiation, proliferation and survival. In the present work, we have developed several strategies to design and prepare synthetic polymeric materials with selected cues to control cell attachment. To promote neuronal cell adhesion on the surfaces, biocompatible, non-adhesive PEG-based materials were modified with neurotransmitter acetylcholine functionalities to produce hydrogels with a range of porous structures, swollen states, and mechanical strengths. Mice hippocampal cells cultured on the hydrogels showed differences in number, length of processes and exhibited different survival rates, thereby highlighting the importance of chemical composition and structure in biomaterials. Similar strategies were used to prepare polymer brushes to assess how topographical cues influence neuronal cell behaviors. The brushes were prepared using the "grown from" method through surface-initiated atom transfer radical polymerization (SI-ATRP) reactions and further patterned via UV photolithography. Protein absorption tests and hippocampal neuronal cell culture of the brush patterns showed that both protein and neuronal cells can adhere to the patterns and therefore can be guided by the patterns at certain length scales. We also prepared functional polymers to discourage attachment of undesirable cells on the surfaces. For example, we synthesized PEG-perfluorinated alkyl amphiphilic surfactants to modify polystyrene-block-poly(ethylene-ran-butylene)- block-polyisoprene (SEBI or K3) triblock copolymers for marine antifouling/fouling release surface coatings. Initial results showed that the polymer coated surfaces can facilitate removal of Ulva sporelings on the surfaces. In addition, we prepared both bioactive and dual functional biopassive/bioactive antimicrobial coatings based on SEBI polymers. Incubating the polymer coated surfaces with gram-positive bacteria (S. aureus), gram-negative bacteria (E. coli) and marine bacteria (C. marina ) species demonstrated that, unlike biopassive surfaces, the dual functionality polymer coated surfaces can significantly reduce both live and dead cells, without killing the cells in the culture media. The knowledge gained from those studies offers opportunities for further modification and potential applications of those types of polymers in the future.

Platinated DNA oligonucleotides: new probes forming ultrastable conjugates with graphene oxide

NASA Astrophysics Data System (ADS)

Wang, Feng; Liu, Juewen

2014-05-01

Metal containing polymers have expanded the property of polymers by involving covalently associated metal complexes. DNA is a special block copolymer. While metal ions are known to influence DNA, little is explored on its polymer property when strong metal complexes are associated. In this work, we study cisplatin modified DNA as a new polymer and probe. Out of the complexes formed between cisplatin-A15, HAuCl4-A15, Hg2+-T15 and Ag+-C15, only the cisplatin adduct is stable under the denaturing gel electrophoresis condition. Each Pt-nucleobase bond gives a positive charge and thus makes DNA a zwitterionic polymer. This allows ultrafast adsorption of DNA by graphene oxide (GO) and the adsorbed complex is highly stable. Non-specific DNA, protein, surfactants and thiolated compounds cannot displace platinated DNA from GO, while non-modified DNA is easily displaced in most cases. The stable GO/DNA conjugate is further tested for surface hybridization. This is the first demonstration of using metallated DNA as a polymeric material for interfacing with nanoscale materials.Metal containing polymers have expanded the property of polymers by involving covalently associated metal complexes. DNA is a special block copolymer. While metal ions are known to influence DNA, little is explored on its polymer property when strong metal complexes are associated. In this work, we study cisplatin modified DNA as a new polymer and probe. Out of the complexes formed between cisplatin-A15, HAuCl4-A15, Hg2+-T15 and Ag+-C15, only the cisplatin adduct is stable under the denaturing gel electrophoresis condition. Each Pt-nucleobase bond gives a positive charge and thus makes DNA a zwitterionic polymer. This allows ultrafast adsorption of DNA by graphene oxide (GO) and the adsorbed complex is highly stable. Non-specific DNA, protein, surfactants and thiolated compounds cannot displace platinated DNA from GO, while non-modified DNA is easily displaced in most cases. The stable GO/DNA conjugate is further tested for surface hybridization. This is the first demonstration of using metallated DNA as a polymeric material for interfacing with nanoscale materials. Electronic supplementary information (ESI) available: Methods, additional gels, kinetics, mass spectrum. See DOI: 10.1039/c4nr00867g

Design and development of low cost polyurethane biopolymer based on castor oil and glycerol for biomedical applications

PubMed Central

Tan, A. C. W.; Polo‐Cambronell, B. J.; Provaggi, E.; Ardila‐Suárez, C.; Ramirez‐Caballero, G. E.; Baldovino‐Medrano, V. G.

2017-01-01

Abstract In the current study, we present the synthesis of novel low cost bio‐polyurethane compositions with variable mechanical properties based on castor oil and glycerol for biomedical applications. A detailed investigation of the physicochemical properties of the polymer was carried out by using mechanical testing, ATR‐FTIR, and X‐ray photoelectron spectroscopy (XPS). Polymers were also tested in short term in‐vitro cell culture with human mesenchymal stem cells to evaluate their biocompatibility for potential applications as biomaterial. FTIR analysis confirmed the synthesis of castor oil and glycerol based PU polymers. FTIR also showed that the addition of glycerol as co‐polyol increases crosslinking within the polymer backbone hence enhancing the bulk mechanical properties of the polymer. XPS data showed that glycerol incorporation leads to an enrichment of oxidized organic species on the surface of the polymers. Preliminary investigation into in vitro biocompatibility showed that serum protein adsorption can be controlled by varying the glycerol content with polymer backbone. An alamar blue assay looking at the metabolic activity of the cells indicated that castor oil based PU and its variants containing glycerol are non‐toxic to the cells. This study opens an avenue for using low cost bio‐polyurethane based on castor oil and glycerol for biomedical applications. PMID:29159831

Interdiffusion of Polycarbonate in Fused Deposition Modeling Welds

NASA Astrophysics Data System (ADS)

Seppala, Jonathan; Forster, Aaron; Satija, Sushil; Jones, Ronald; Migler, Kalman

2015-03-01

Fused deposition modeling (FDM), a now common and inexpensive additive manufacturing method, produces 3D objects by extruding molten polymer layer-by-layer. Compared to traditional polymer processing methods (injection, vacuum, and blow molding), FDM parts have inferior mechanical properties, surface finish, and dimensional stability. From a polymer processing point of view the polymer-polymer weld between each layer limits the mechanical strength of the final part. Unlike traditional processing methods, where the polymer is uniformly melted and entangled, FDM welds are typically weaker due to the short time available for polymer interdiffusion and entanglement. To emulate the FDM process thin film bilayers of polycarbonate/d-polycarbonate were annealed using scaled times and temperatures accessible in FDM. Shift factors from Time-Temperature Superposition, measured by small amplitude oscillatory shear, were used to calculate reasonable annealing times (min) at temperatures below the actual extrusion temperature. The extent of interdiffusion was then measured using neutron reflectivity. Analogous specimens were prepared to characterize the mechanical properties. FDM build parameters were then related to interdiffusion between welded layers and mechanical properties. Understating the relationship between build parameters, interdiffusion, and mechanical strength will allow FDM users to print stronger parts in an intelligent manner rather than using trial-and-error and build parameter lock-in.

Emulsion-Based RIR-MAPLE Deposition of Conjugated Polymers: Primary Solvent Effect and Its Implications on Organic Solar Cell Performance.

PubMed

Ge, Wangyao; Li, Nan K; McCormick, Ryan D; Lichtenberg, Eli; Yingling, Yaroslava G; Stiff-Roberts, Adrienne D

2016-08-03

Emulsion-based, resonant infrared matrix-assisted pulsed laser evaporation (RIR-MAPLE) has been demonstrated as an alternative technique to deposit conjugated polymer films for photovoltaic applications; yet, a fundamental understanding of how the emulsion target characteristics translate into film properties and solar cell performance is unclear. Such understanding is crucial to enable the rational improvement of organic solar cell (OSC) efficiency and to realize the expected advantages of emulsion-based RIR-MAPLE for OSC fabrication. In this paper, the effect of the primary solvent used in the emulsion target is studied, both experimentally and theoretically, and it is found to determine the conjugated polymer cluster size in the emulsion as well as surface roughness and internal morphology of resulting polymer films. By using a primary solvent with low solubility-in-water and low vapor pressure, the surface roughness of deposited P3HT and PCPDTBT polymer films was reduced to 10 nm, and the efficiency of P3HT:PC61BM OSCs was increased to 3.2% (∼100 times higher compared to the first MAPLE OSC demonstration [ Caricato , A. P. ; Appl. Phys. Lett. 2012 , 100 , 073306 ]). This work unveils the mechanism of polymer film formation using emulsion-based RIR-MAPLE and provides insight and direction to determine the best ways to take advantage of the emulsion target approach to control film properties for different applications.

Analysis of liquid-phase chemical detection using guided shear horizontal-surface acoustic wave sensors.

PubMed

Li, Zhonghui; Jones, Yolanda; Hossenlopp, Jeanne; Cernosek, Richard; Josse, Fabien

2005-07-15

Direct chemical sensing in liquid environments using polymer-guided shear horizontal surface acoustic wave sensor platforms on 36 degrees rotated Y-cut LiTaO3 is investigated. Design considerations for optimizing these devices for liquid-phase detection are systematically explored. Two different sensor geometries are experimentally and theoretically analyzed. Dual delay line devices are used with a reference line coated with poly (methyl methacrylate) (PMMA) and a sensing line coated with a chemically sensitive polymer, which acts as both a guiding layer and a sensing layer or with a PMMA waveguide and a chemically sensitive polymer. Results show the three-layer model provides higher sensitivity than the four-layer model. Contributions from mass loading and coating viscoelasticity changes to the sensor response are evaluated, taking into account the added mass, swelling, and plasticization. Chemically sensitive polymers are investigated in the detection of low concentrations (1-60 ppm) of toluene, ethylbenzene, and xylenes in water. A low-ppb level detection limit is estimated from the present experimental measurements. Sensor properties are investigated by varying the sensor geometries, coating thickness combinations, coating properties, and curing temperature for operation in liquid environments. Partition coefficients for polymer-aqueous analyte pairs are used to explain the observed trend in sensitivity for the polymers PMMA, poly(isobutylene), poly(epichlorohydrin), and poly(ethyl acrylate) used in this work.

Plasma immersion ion implantation of polyurethane shape memory polymer: Surface properties and protein immobilization

NASA Astrophysics Data System (ADS)

Cheng, Xinying; Kondyurin, Alexey; Bao, Shisan; Bilek, Marcela M. M.; Ye, Lin

2017-09-01

Polyurethane-type shape memory polymers (SMPU) are promising biomedical implant materials due to their ability to recover to a predetermined shape from a temporary shape induced by thermal activation close to human body temperature and their advantageous mechanical properties including large recovery strains and low recovery stresses. Plasma Immersion Ion Implantation (PIII) is a surface modification process using energetic ions that generates radicals in polymer surfaces leading to carbonisation and oxidation and the ability to covalently immobilise proteins without the need for wet chemistry. Here we show that PIII treatment of SMPU significantly enhances its bioactivity making SMPU suitable for applications in permanent implantable biomedical devices. Scanning Electron Microscopy (SEM), contact angle measurements, surface energy measurements, attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterise the PIII modified surface, including its after treatment aging kinetics and its capability to covalently immobilise protein directly from solution. The results show a substantial improvement in wettability and dramatic changes of surface chemical composition dependent on treatment duration, due to the generation of radicals and subsequent oxidation. The SMPU surface, PIII treated for 200s, achieved a saturated level of covalently immobilized protein indicating that a full monolayer coverage was achieved. We conclude that PIII is a promising and efficient surface modification method to enhance the biocompatibility of SMPU for use in medical applications that demand bioactivity for tissue integration and stability in vivo.

Structure and rheology of star polymers in confined geometries: a mesoscopic simulation study.

PubMed

Zheng, Feiwo; Goujon, Florent; Mendonça, Ana C F; Malfreyt, Patrice; Tildesley, Dominic J

2015-11-28

Mesoscopic simulations of star polymer melts adsorbed onto solid surfaces are performed using the dissipative particle dynamics (DPD) method. A set of parameters is developed to study the low functionality star polymers under shear. The use of a new bond-angle potential between the arms of the star creates more rigid chains and discriminates between different functionalities at equilibrium, but still allows the polymers to deform appropriately under shear. The rheology of the polymer melts is studied by calculating the kinetic friction and viscosity and there is good agreement with experimental properties of these systems. The study is completed with predictive simulations of star polymer solutions in an athermal solvent.

Ultrathin Polymer Films, Patterned Arrays, and Microwells

NASA Astrophysics Data System (ADS)

Yan, Mingdi

2002-05-01

The ability to control and tailor the surface and interface properties of materials is important in microelectronics, cell growth control, and lab-on-a-chip devices. Modification of material surfaces with ultrathin polymer films is attractive due to the availability of a variety of polymers either commercially or by synthesis. We have developed two approaches to the attachment of ultrathin polymer films on solid substrates. In the first method, a silane-functionalized perfluorophenyl azide (PFPA-silane) was synthesized and used to covalently immobilize polymer thin films on silicon wafers. Silanization of the wafer surface with the PFPA-silane introduced a monolayer of azido groups which in turn covalently attached the polymer film by way of photochemically initiated insertion reactions. The thickness of the film could be adjusted by the type and the molecular weight of the polymer. The method is versatile due to the general C-H and/or N-H insertion reactions of crosslinker; and therefore, no specific reactive functional groups on the polymers are required. Using this method, a new type of microwell array was fabricated from covalently immobilized polymer thin films on flat substrates. The arrays were characterized with AFM, XPS, and TOF-SIMS. The second method describes the attachment of polymer thin films on solid substrates via UV irradiation. The procedure consisted of spin-coating a polymer film and irradiating the film with UV light. Following solvent extraction, a thin film remained. The thickness of the film, from a few to over a hundred nanometers, was controlled by varying solution concentration and the molecular weight of the polymer.

A facile fabrication of multifunctional knit polyester fabric based on chitosan and polyaniline polymer nanocomposite

NASA Astrophysics Data System (ADS)

Tang, Xiaoning; Tian, Mingwei; Qu, Lijun; Zhu, Shifeng; Guo, Xiaoqing; Han, Guangting; Sun, Kaikai; Hu, Xili; Wang, Yujiao; Xu, Xiaoqi

2014-10-01

Knit polyester fabric was successively modified and decorated with chitosan layer and polyaniline polymer nanocomposite layer in this paper. The fabric was firstly treated with chitosan to form a stable layer through the pad-dry-cure process, and then the polyaniline polymer nanocomposite layer was established on the outer layer by in situ chemical polymerization method using ammonium persulfate as oxidant and chlorhydric acid as dopant. The surface morphology of coated fabric was characterized by scanning electron microscopy (SEM), and the co-existence of chitosan layer and granular polyaniline polymer nanocomposite was confirmed and well dispersed on the fabric surface. The resultant fabric was endowed with remarkable electrical conductivity properties and efficient water-repellent capability, which also have been found stable after water laundering. In addition, the photocatalytic decomposition activity for reactive red dye was observed when the multifunctional knit polyester fabric was exposed to the illumination of ultraviolet lamp. These results indicated that chitosan and polyaniline polymer nanocomposite could form ideal multifunctional coatings on the surface of knit polyester fabric.

Conducting Polymer Nanostructures: Template Synthesis and Applications in Energy Storage

PubMed Central

Pan, Lijia; Qiu, Hao; Dou, Chunmeng; Li, Yun; Pu, Lin; Xu, Jianbin; Shi, Yi

2010-01-01

Conducting polymer nanostructures have received increasing attention in both fundamental research and various application fields in recent decades. Compared with bulk conducting polymers, conducting polymer nanostructures are expected to display improved performance in energy storage because of the unique properties arising from their nanoscaled size: high electrical conductivity, large surface area, short path lengths for the transport of ions, and high electrochemical activity. Template methods are emerging for a sort of facile, efficient, and highly controllable synthesis of conducting polymer nanostructures. This paper reviews template synthesis routes for conducting polymer nanostructures, including soft and hard template methods, as well as its mechanisms. The application of conducting polymer mesostructures in energy storage devices, such as supercapacitors and rechargeable batteries, are discussed. PMID:20717527

Conducting polymer nanostructures: template synthesis and applications in energy storage.

PubMed

Pan, Lijia; Qiu, Hao; Dou, Chunmeng; Li, Yun; Pu, Lin; Xu, Jianbin; Shi, Yi

2010-07-02

Conducting polymer nanostructures have received increasing attention in both fundamental research and various application fields in recent decades. Compared with bulk conducting polymers, conducting polymer nanostructures are expected to display improved performance in energy storage because of the unique properties arising from their nanoscaled size: high electrical conductivity, large surface area, short path lengths for the transport of ions, and high electrochemical activity. Template methods are emerging for a sort of facile, efficient, and highly controllable synthesis of conducting polymer nanostructures. This paper reviews template synthesis routes for conducting polymer nanostructures, including soft and hard template methods, as well as its mechanisms. The application of conducting polymer mesostructures in energy storage devices, such as supercapacitors and rechargeable batteries, are discussed.

Salt-responsive polyzwitterionic materials for surface regeneration between switchable fouling and antifouling properties.

PubMed

Chen, Hong; Yang, Jintao; Xiao, Shengwei; Hu, Rundong; Bhaway, Sarang M; Vogt, Bryan D; Zhang, Mingzhen; Chen, Qiang; Ma, Jie; Chang, Yung; Li, Lingyan; Zheng, Jie

2016-08-01

Development of smart regenerative surface is a highly challenging but important task for many scientific and industrial applications. Specifically, very limited research efforts were made for surface regeneration between bio-adhesion and antifouling properties, because bioadhesion and antifouling are the two highly desirable but completely opposite properties of materials. Herein, we developed salt-responsive polymer brushes of poly(3-(1-(4-vinylbenzyl)-1H-imidazol-3-ium-3-yl) propane-1-sulfonate) (polyVBIPS), which can be switched reversibly and repeatedly between protein capture/release and surface wettability in a controllable manner. PolyVBIPS brush has demonstrated its switching ability to resist both protein adsorption from 100% blood plasma/serum and bacterial attachment in multiple cycles. PolyVBIPS brush also exhibits reversible surface wettability from ∼40° to 25° between in PBS and in 1M NaCl solutions in multiple cycles. Overall, the salt-responsive behaviors of polyVBIPS brushes can be interpreted by the "anti-polyelectrolyte effect", i.e. polyVBIPS brushes adopt a collapsed chain conformation at low ionic strengths to achieve surface adhesive, but an extended chain conformation at high ionic strength to realize antifouling properties. We expect that polyVBIPS will provide a simple, robust, and promising system for the fabrication of smart surfaces with biocompatible, reliable, and regenerative properties. Unlike many materials with "one-time switching" capability for surface regeneration, we developed a new regenerative surface of zwitterionic polymer brush, which exhibits a reversible salt-induced switching property between a biomolecule-adhesive state and a biomolecule repellent state in complex media for multiple cycles. PolyVBIPS is easily synthesized and can be straightforward coated on the surface, which provides a simple, robust, and promising system for the fabrication of smart surfaces with biocompatible, reliable, regenerative properties. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Tuning Glass Transition in Polymer Nanocomposites with Functionalized Cellulose Nanocrystals through Nanoconfinement.

PubMed

Qin, Xin; Xia, Wenjie; Sinko, Robert; Keten, Sinan

2015-10-14

Cellulose nanocrystals (CNCs) exhibit impressive interfacial and mechanical properties that make them promising candidates to be used as fillers within nanocomposites. While glass-transition temperature (Tg) is a common metric for describing thermomechanical properties, its prediction is extremely difficult as it depends on filler surface chemistry, volume fraction, and size. Here, taking CNC-reinforced poly(methyl-methacrylate) (PMMA) nanocomposites as a relevant model system, we present a multiscale analysis that combines atomistic molecular dynamics (MD) surface energy calculations with coarse-grained (CG) simulations of relaxation dynamics near filler-polymer interfaces to predict composite properties. We discover that increasing the volume fraction of CNCs results in nanoconfinement effects that lead to an appreciation of the composite Tg provided that strong interfacial interactions are achieved, as in the case of TEMPO-mediated surface modifications that promote hydrogen bonding. The upper and lower bounds of shifts in Tg are predicted by fully accounting for nanoconfinement and interfacial properties, providing new insight into tuning these aspects in nanocomposite design. Our multiscale, materials-by-design framework is validated by recent experiments and breaks new ground in predicting, without any empirical parameters, key structure-property relationships for nanocomposites.

Fix it first : utilizing the seismic property analyzer and MMLS to develop guidelines for the use of polymer modified thin lift HMA vs. surface treatments.

DOT National Transportation Integrated Search

2012-09-01

The main objective of this study was to develop thin lift overlay mixtures with polymer modified asphalt for use in New England. As part of this : research a comprehensive literature review and internet survey was conducted. Moreover, laboratory test...

Characterization of plasticized PEO-PAM blend polymer electrolyte system

NASA Astrophysics Data System (ADS)

Dave, Gargi; Kanchan, Dinesh

2017-05-01

Present study reports characterization studies of NaCF3SO3 based PEO-PAM Blend Polymer Electrolyte (BPE) system with varying amount of EC+PC as plasticizer prepared by solution cast technique. Structural analysis and surface topography have been performed using FTIR and SEM studies. To understand, thermal properties, DSC studies have been undertaken in the present paper

Mechanical properties and surface chemistry of kenaf fiber for composite reinforcement – an insight into the retting process

USDA-ARS?s Scientific Manuscript database

Harnessing natural fibers to produce polymer composites requires processing of fibers from harvest to the dried state, which can then be dispersed in the polymer resin. Bast fibers are found in the bark layer of fibrous plants such as kenaf (Hibiscus cannabinus), jute (Corchorus olitorius), and flax...

Characterization of biodegradable polymers irradiated with swift heavy ions

NASA Astrophysics Data System (ADS)

Salguero, N. G.; del Grosso, M. F.; Durán, H.; Peruzzo, P. J.; Amalvy, J. I.; Arbeitman, C. R.; García Bermúdez, G.

2012-02-01

In view of their application as biomaterials, there is an increasing interest in developing new methods to induce controlled cell adhesion onto polymeric materials. The critical step in all these methods involves the modification of polymer surfaces, to induce cell adhesion, without changing theirs degradation and biocompatibility properties. In this work two biodegradable polymers, polyhydroxybutyrate (PHB) and poly- L-lactide acid (PLLA) were irradiated using carbon and sulfur beams with different energies and fluences. Pristine and irradiated samples were degradated by immersion in a phosphate buffer at pH 7.0 and then characterized. The analysis after irradiation and degradation showed a decrease in the contact angle values and changes in their crystallinity properties.

The properties of the wood-polystyrene interphase determined by inverse gas chromatography

Treesearch

John Simonsen; Zhenqiu Hong; Timothy G. Rials

1997-01-01

The properties of the interphase in wood-polymer composites are important determinants of the properties of the final composite. This study used inverse gas chromatography (IGC) to measure interphasal properties of composites of polystyrene and two types of wood fiber fillers and an inoranic substrate (CW) with varying amounts of surface coverage of polystyrene. Glass...

Photonic polymer-blend structures and method for making

DOEpatents

Barnes, Michael D.

2004-06-29

The present invention comprises the formation of photonic polymer-blend structures having tunable optical and mechanical properties. The photonic polymer-blend structures comprise monomer units of spherical microparticles of a polymer-blend material wherein the spherical microparticles have surfaces partially merged with one another in a robust inter-particle bond having a tunable inter-particle separation or bond length sequentially attached in a desired and programmable architecture. The photonic polymer-blend structures of the present invention can be linked by several hundred individual particles sequentially linked to form complex three-dimensional structures or highly ordered two-dimensional arrays of 3D columns with 2D spacing.

Quantitative estimation of film forming polymer-plasticizer interactions by the Lorentz-Lorenz Law.

PubMed

Dredán, J; Zelkó, R; Dávid, A Z; Antal, I

2006-03-09

Molar refraction as well as refractive index has many uses. Beyond confirming the identity and purity of a compound, determination of molecular structure and molecular weight, molar refraction is also used in other estimation schemes, such as in critical properties, surface tension, solubility parameter, molecular polarizability, dipole moment, etc. In the present study molar refraction values of polymer dispersions were determined for the quantitative estimation of film forming polymer-plasticizer interactions. Information can be obtained concerning the extent of interaction between the polymer and the plasticizer from the calculation of molar refraction values of film forming polymer dispersions containing plasticizer.

Preparation of protein- and cell-resistant surfaces by hyperthermal hydrogen induced cross-linking of poly(ethylene oxide).

PubMed

Bonduelle, Colin V; Lau, Woon M; Gillies, Elizabeth R

2011-05-01

The functionalization of surfaces with poly(ethylene oxide) (PEO) is an effective means of imparting resistance to the adsorption of proteins and the attachment and growth of cells, properties that are critical for many biomedical applications. In this work, a new hyperthermal hydrogen induced cross-linking (HHIC) method was explored as a simple one-step approach for attaching PEO to surfaces through the selective cleavage of C-H bonds and subsequent cross-linking of the resulting carbon radicals. In order to study the effects of the process on the polymer, PEO-coated silicon wafers were prepared and the effects of different treatment times were investigated. Subsequently, using an optimized treatment time and a modified butyl polymer with increased affinity for PEO, the technique was applied to butyl rubber surfaces. All of the treated surfaces exhibited significantly reduced protein adsorption and cell growth relative to control surfaces and compared favorably with surfaces that were functionalized with PEO using conventional chemical methods. Thus HHIC is a simple and effective means of attaching PEO to non-functional polymer surfaces.

Probing the structural dependence of carbon space lengths of poly(N-hydroxyalkyl acrylamide)-based brushes on antifouling performance.

PubMed

Yang, Jintao; Zhang, Mingzhen; Chen, Hong; Chang, Yung; Chen, Zhan; Zheng, Jie

2014-08-11

Numerous biocompatible antifouling polymers have been developed for a wide variety of fundamental and practical applications in drug delivery, biosensors, marine coatings, and many other areas. Several antifouling mechanisms have been proposed, but the exact relationship among molecular structure, surface hydration property, and antifouling performance of antifouling polymers still remains elusive. Here this work strives to provide a better understanding of the structure-property relationship of poly(N-hydroxyalkyl acrylamide)-based materials. We have designed, synthesized, and characterized a series of polyHAAA brushes of various carbon spacer lengths (CSLs), that is, poly(N-hydroxymethyl acrylamide) (polyHMAA), poly(N-(2-hydroxyethyl)acrylamide) (polyHEAA), poly(N-(3-hydroxypropyl)acrylamide) (polyHPAA), and poly(N-(5-hydroxypentyl)acrylamide) (polyHPenAA), to study the structural dependence of CSLs on their antifouling performance. HMAA, HEAA, HPAA, and HPenAA monomers contained one, two, three, and five methylene groups between hydroxyl and amide groups, while the other groups in polymer backbones were the same as each other. The relation of such small structural differences of polymer brushes to their surface hydration and antifouling performance was studied by combined experimental and computational methods including surface plasmon resonance sensors, sum frequency generation (SFG) vibrational spectroscopy, cell adhesion assay, and molecular simulations. Antifouling results showed that all polyHAAA-based brushes were highly surface resistant to protein adsorption from single protein solutions, undiluted blood serum and plasma, as well as cell adhesion up to 7 days. In particular, polyHMAA and polyHEAA with the shorter CSLs exhibited higher surface hydration and better antifouling ability than polyHPMA and polyHPenAA. SFG and molecular simulations further revealed that the variation of CSLs changed the ratio of hydrophobicity/hydrophilicity of polymers, resulting in different hydration characteristics. Among them, polyHMAA and polyHEAA with the shorter CSLs showed the highest potency for surface hydration and antifouling abilities, while polyHPenAA showed the lowest potency. The combination of both hydroxyl and amide groups in the same polymer chain provides a promising structural motif for the design of new effective antifouling materials.

Thermal Spraying of Bioactive Polymer Coatings for Orthopaedic Applications

NASA Astrophysics Data System (ADS)

Chebbi, A.; Stokes, J.

2012-06-01

Flame sprayed biocompatible polymer coatings, made of biodegradable and non-biodegradable polymers, were investigated as single coatings on titanium and as top coatings on plasma sprayed Hydroxyapatite. Biocompatible polymers can act as drug carriers for localized drug release following implantation. The polymer matrix consisted of a biodegradable polymer, polyhydroxybutyrate 98%/ polyhydroxyvalerate 2% (PHBV) and a non-biodegradable polymer, polymethylmethacrylate (PMMA). Screening tests were performed to determine the suitable range of spraying parameters, followed by a Design of Experiments study to determine the effects of spraying parameters on coating characteristics (thickness, roughness, adhesion, wettability), and to optimize the coating properties accordingly. Coatings characterization showed that optimized flame sprayed biocompatible polymers underwent little chemical degradation, did not produce acidic by-products in vitro, and that cells proliferated well on their surface.

Sodium dodecyl sulfate-ethoxylated polyethylenimine adsorption at the air-water interface: how the nature of ethoxylation affects the pattern of adsorption.

PubMed

Batchelor, Stephen N; Tucker, Ian; Petkov, Jordan T; Penfold, Jeffrey; Thomas, Robert K

2014-08-19

The strong interaction between ionic surfactants and polyelectrolytes of opposite charge results in enhanced surface adsorption at the air-water interface down to low surfactant concentrations and in some cases in the formation of ordered surface structures. A notable example which exhibits such properties is the mixture of polyethylenimine, PEI, and sodium dodecyl sulfate, SDS. However, the electrostatic interaction, around charge neutralization, between the surfactant and polymer often results in precipitation or coacervation. This can be mitigated for PEI-surfactant mixtures by ethoxylation of the PEI, but this can also result in a weaker surface interaction and a significant reduction in the adsorption. It is shown here that by localizing the ethoxylation of the PEI into discrete regions of the polymer precipitation upon the addition of SDS is suppressed, the strong surface interaction and enhanced adsorption of the polymer-surfactant mixture is retained. The adsorption of SDS in the presence of ethoxylated PEI is greatly enhanced at low SDS concentrations compared to the adsorption for pure SDS. The adsorption is equally pronounced at pH 7 and 10 and is largely independent of the degree of ethoxylation. Surface ordering, more than monolayer adsorption, is observed over a relatively narrow range of SDS concentrations and is most pronounced at pH 10 and for the polymers with the lower degree of ethoxylation. The results show that ethoxylated PEI's reported here provide a suitable route to enhanced surfactant adsorption while retaining favorable solution properties in which precipitation effects are minimized.

Physicochemical properties and cytotoxicity of hydrogels based on Beetosan® containing sage and bee pollen.

PubMed

Tyliszczak, Bożena; Drabczyk, Anna; Kudłacik-Kramarczyk, Sonia; Grabowska, Beata; Kędzierska, Magdalena

2017-01-01

Currently, increasing attention is being paid to issues related to environmental protection, waste management, as well as to the development of polymers with useful properties. The research presented here involved preparation of hydrogels based on Beetosan® - a chitosan derived from the multi-stage processing of dead bees. Moreover, hydrogels were additionally modified with natural substances - i.e. bee pollen and extract of Salvia officinalis (sage) that are well known for the presence of many compounds with beneficial properties from a medical point of view. Materials have been first obtained by photopolymerization. Then, their surface morphology, wettability and cytotoxicity to selected cell lines have been determined. It can be stated that such combination of Beetosan® hydrogel matrix and the mentioned additives resulted in a preparation of polymers characterized by negative impact on cancer cells. Impact of hydrogels with sage is slightly more intense due to the presence of substances such as ursalic or rosmaric acid that are characterized to have anticancer activity. Such negative impact has not been observed in case of studies using fibroblasts. Furthermore, addition of natural substances into hydrogels resulted in a more homogeneous surface and in the decrease of wettability angle of the tested polymers. It can be concluded that the use of natural-derived reagents and synthesis of polymers using these reagents (as a result of environmentally friendly photopolymerization) yields materials with interesting properties for medical purposes, with particular emphasis on antitumor activity, and without significant negative impact on fibroblasts.

Characterization and mechanism of He plasma pretreatment of nanoscale polymer masks for improved pattern transfer fidelity

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

Weilnboeck, F.; Metzler, D.; Kumar, N.

2011-12-26

Roughening of nanoscale polymer masks during plasma etching (PE) limits feature critical dimensions in current and future lithographic technologies. Roughness formation of 193 nm photoresist (PR) is mechanistically explained by plasma-induced changes in mechanical properties introduced at the PR surface ({approx}2 nm) by ions and in parallel in the material bulk ({approx}200 nm) by ultraviolet (UV) plasma radiation. Synergistic roughening of polymer masks can be prevented by pretreating PR patterns with a high dose of He plasma UV exposure to saturate bulk material modifications. During subsequent PE, PR patterns are stabilized and exhibit improved etch resistance and reduced surface/line-edge roughness.

Preparation and evaluation of posaconazole-loaded enteric microparticles in rats.

PubMed

Yang, Min; Dong, Zhonghua; Zhang, Yongchun; Zhang, Fang; Wang, Yongjie; Zhao, Zhongxi

2017-04-01

Posaconazole (POS) is an antifungal compound which has a low oral bioavailability. The aim of this study was to prepare POS enteric microparticles to enhance its oral bioavailability. POS enteric microparticles were prepared with hypromellose acetate succinate (HPMCAS) via the spray drying method. The solvent mixtures of acetone and ethanol used in the preparation of the microparticles were optimized to produce the ideal POS enteric microparticles. Multivariate data analysis using a principal component analysis (PCA) was used to find the relationship among the HPMCAS molecular characteristics, particle properties and drug release kinetics from the spray dried microparticles. The optimal spray solvent mixtures were critical to produce the POS microparticles with the defined polymer entanglement index, drug surface enrichment, particle size and drug loading. The HPMCAS molecular characteristics affected the microscopic connectivity and diffusivity of polymer matrix and eventually influenced the drug release behavior, and enhanced the bioavailability of POS. These studies suggested that the selection of suitable solvent mixtures of acetone and ethanol used in the spray drying of the microparticles was quite important to produce the entangled polymer structures with preferred polymer molecular properties of polymer coiling, overlap concentration and entanglement index. Additional studies on particle size and surface drug enrichment eventually produced HPMCAS-based enteric microparticles to enhance the oral bioavailability of POS.

Influence of Mold Surface Treatments on Flow of Polymer in Injection Moulding. Application to Weldlines

NASA Astrophysics Data System (ADS)

Chailly, M.; Charmeau, J.-Y.; Bereaux, Y.; Monasse, B.

2007-04-01

Due to increasing expectations from the market, the aspect of molded parts has to be improved constantly. Some of the defects observed on these parts such as weldlines are related to the filling stage. To limit this, we investigated the influence on weldlines using various surface deposits on the mold surface, mainly PVD and PACVD deposits : Chromium nitride (CrN), Titanium nitride (TiN), Diamond like Carbon (DLC), Chromium and polished steel (PG) on an instrumented plate mold. Injection campaign was led on three polymers which differ in terms of nature (amorphous, semi-crystalline, copolymers). We studied the evolution of the dimensions of weldlines appearing on the plate using the same injection parameters for a given polymer, but with various deposits and thicknesses. Another aspect that had been investigated is the morphology of the weldline through the thickness of the part, depending on polymer nature. Adhesion of polymer at the flow front with the mold surface proved to change. The modification of the initial contact in the filling stage and thus the thermal resistance at the mold implied a change in the process, increasing or reducing the pressure loss in the flow and differential shrinkage in the final part. The induced impact on dimensions of the weldlines allowed to distinguish which surface treatments were able to reduce the defect. A complementary study was led on both polymers in molten state and deposits in terms of wetting using a sessile drop method to confirm the adhesion at the polymer/mold interface. This study proved the influence of the use of surface treatments has clearly an impact on the filling stage of the injection molding process, and it is necessary to get a better knowledge of the interactions between physical adhesion, tribology of polymer/mold contact, and thermal properties of the coatings and their impact on solidification of the polymer.

Supramolecular Polymer Nanocomposites - Improvement of Mechanical Properties

NASA Astrophysics Data System (ADS)

Hinricher, Jesse; Neikirk, Colin; Priestley, Rodney

2015-03-01

Supramolecular polymers differ from traditional polymers in that their repeat units are connected by hydrogen bonds that can reversibly break and form under various stimuli. They can be more easily recycled than conventional materials, and their highly temperature dependent viscosities result in reduced energy consumption and processing costs. Furthermore, judicious selection of supramolecular polymer architecture and functionality allows the design of advanced materials including shape memory and self-healing materials. Supramolecular polymers have yet to see widespread use because they can't support much weight due to their inherent mechanical weakness. In order to address this issue, the mechanical strength of supramolecular polymer nanocomposites based on ureidopyrmidinone (UPy) telechelic poly(caprolactone) doped with surface activated silica nanoparticles was investigated by tensile testing and dynamic mechanical analysis. The effects of varying amounts and types of nanofiller surface functionality were investigated to glean insight into the contributions of filler-filler and filler-matrix interactions to mechanical reinforcement in supramolecular polymer nanocomposites. MRSEC NSF DMR 0819860 (PI: Prof. N. Phuan Ong) REU Site Grant: NSF DMR-1156422 (PI: Prof. Mikko Haataja)

How the Dynamics of a Supramolecular Polymer Determines Its Dynamic Adaptivity and Stimuli-Responsiveness: Structure-Dynamics-Property Relationships From Coarse-Grained Simulations.

PubMed

Torchi, Andrea; Bochicchio, Davide; Pavan, Giovanni M

2018-04-12

The rational design of supramolecular polymers that can adapt or respond in time to specific stimuli in a controlled way is interesting for many applications, but this requires understanding the molecular factors that make the material faster or slower in responding to the stimulus. To this end, it is necessary to study the dynamic adaptive properties at submolecular resolution, which is difficult at an experimental level. Here we show coarse-grained molecular dynamics simulations (<5 Å resolution) demonstrating how the dynamic adaptivity and stimuli responsiveness of a supramolecular polymer is controlled by the intrinsic dynamics of the assembly, which is in turn determined by the structure of the monomers. As a representative case, we focus on a water-soluble 1,3,5-benzenetricarboxamide (BTA) supramolecular polymer incorporating (charged) receptor monomers, experimentally seen to undergo dynamic clustering following the superselective binding to a multivalent recruiter. Our simulations show that the dynamic reorganization of the supramolecular structure proceeds via monomer diffusion on the dynamic fiber surface (exchange within the fiber). Rationally changing the structure of the monomers to make the fiber surface more or less dynamic allows tuning the rate of response to the stimulus and of supramolecular reconfiguration. Simple in silico experiments draw a structure-dynamics-property relationship revealing the key factors underpinning the dynamic adaptivity and stimuli-responsiveness of these supramolecular polymers. We come out with clear evidence that to master the bioinspired properties of these fibers, it is necessary to control their intrinsic dynamics, while the high-resolution of our molecular models permits us to show how.

Biocompatibility of modified ultra-high-molecular-weight polyethylene

NASA Astrophysics Data System (ADS)

Novotná, Z.; Lacmanová, V.; Rimpelová, S.; Juřik, P.; Polívková, M.; Å vorčik, V.

2016-09-01

Ultra-high-molecular-weight polyethylene (UHMWPE, PE) is a synthetic polymer used for biomedical applications because of its high impact resistance, ductility and stability in contact with physiological fluids. Therefore this material is being used in human orthopedic implants such as total joint replacements. Surface modification of this material relates to changes of its surface hydrophilicity, energy, microstructure, roughness, and morphology, all influencing its biological response. In our recent work, PE was treated by an Ar+ plasma discharge and then grafted with biologically active polyethylene glycol in order to enhance adhesion and proliferation of mouse fibroblast (L929). The surface properties of pristine PE and its grafted counterparts were studied by goniometry (surface wettability). Furthermore, Atomic Force Microscopy was used to determine the surface morphology and roughness. The biological response of the L929 cell lines seeded on untreated and plasma treated PE matrices was quantified in terms of the cell adhesion, density, and metabolic activity. Plasma treatment leads to the ablation of the polymer surface layers. Plasma treatment and subsequent poly(ethylene glycol) grafting lead to dramatic changes in the polymer surface morphology and roughness. Biological tests, performed in vitro, show increased adhesion and proliferation of cells on modified polymers. Grafting with poly(ethylene glycol) increases cell proliferation compared to plasma treatment.

Photoluminescence of Co: ZnNiO and Zr: ZnNiO nanocomposites capped with biodegradable polymer poly (2-ethyl-2-oxazoline)

NASA Astrophysics Data System (ADS)

John, Sam; George, James Baben; Joseph, Abraham

2018-05-01

The optical properties of the semiconducting nanomaterials has a wide variety of applications in the biological and industrial fields, which include the synthesis of UV laser, light emitting diodes, solar cells, gas sensors, piezoelectric transducers etc. Among the various types of optical properties, luminescence especially photoluminescence (PL) of metal oxides are more prominently studied. This is because PL spectrum is an effective way to investigate the electronic structure, optical and photochemical properties of semiconductor materials which deciphers information such as surface oxygen vacancies, defects, efficiency of charge carrier trapping, immigration, transfer etc. To overcome the drawbacks in luminescence studies of metal oxide nanomaterials, polymer technology has also been incorporated. The scientists found that the doping of some elements into the polymer capped ZnO nanocomposites enhanced the luminescence properties of the compound. In the current study, we are investigating the photoluminescence properties of ZnO nanocomposites capped with a biodegradable polymer poly (2-ethyl 2-oxazoline) and doped with the elements Cobalt and Zirconium. We obtained many strong fluorescence peaks in the visible and UV regions in the PL spectrum and UV absorption spectroscopy.

Synthesis and applications of titania nanotubes: Drug delivery and ionomer composites

NASA Astrophysics Data System (ADS)

Kulkarni, Harsha Prabhakar

In this dissertation, the potential of a tubular form of titania (titanium dioxide) has been explored for two diverse applications, in the field of targeted drug delivery for medical applications and in the field of composite materials for structural applications. We introduce the tubular form of titania, a material well known for its catalytic properties. The tubes are synthesized by hydrothermal procedure and are nanometers in dimension, with an inside diameter of 5-6 nm, outside diameter of 10-12, and an aspect ratio of ˜100:1 (l:d), structures both chemically and thermally stable. Biocompatible titania nanotubes with large catalytic surface area are used as vehicles for carrying Doxorubicin, an anticancer chemotherapeutic drug, to explore its potential in targeted drug delivery. Optical properties of Doxorubicin are used to study adsorption and release of the drug molecule from the nanotube surface. Pilot experiments show strong adsorption of 4 wt% of doxorubicin on the nanotube surface characterized by the quenching of its absorption centered at 490 nm. Quinone and protonated amino groups on the drug molecule, involved in protonation and deprotonation with the surface hydroxyls and molecular water on the nanotube surface, are responsible for adsorption. Doxorubicin adsorbed on the nanotube surface show pH specific release, with 40% release at a physiological pH of 7.4 as compared to 4% and 10% at pH values of 3.4 and 5.7 respectively under sink conditions. In vitro cytotoxicity experiments, used to characterize the anticancer potential of the nanotube-drug conjugate, shows comparable toxicity for the conjugates as the free drug. Nanotubes with strong adsorption of doxorubicin, large surface area, pH controlled release, and effective toxicity, demonstrate its potential as a vehicle for targeted drug delivery. If nanotube-drug conjugates with reversible bonds between them, and a pH controlled release in an aqueous solution are promising for medical applications, nanotube-polymer conjugates with nanotubes as reinforcing structures in a polymer matrix with improved mechanical properties are equally promising for structural applications. Nanotubes are used as reinforcing structures in Surlyn, a polyethylene-co-methacrylic acid polymer containing ions. When cooled from the melt, Surlyn shows strong aging effects on mechanical properties over periods of several days to months. Structures in the matrix of the polymer which form with time are responsible for these aging effects on mechanical properties. Aging at short times after cooling from the melt reveal subtle contributions from these structures not fully formed and mechanical properties not fully recovered. Nanotubes are used as reinforcing structures to improve the mechanical properties at short aging times, a property desired for high temperature applications demanding a quick recovery of mechanical properties. A unique Atomic Force Microscope (AFM) based Local Thermal Analysis (LTA) probe is used to study the mechanical properties of Surlyn and Nanotube-Surlyn composite. Nanotube-Surlyn composites show superior mechanical properties at both short and long aging times after cooling from the melt, as the structures in the matrix continue to form at long aging times.

Visualization of Au Nanoparticles Buried in a Polymer Matrix by Scanning Thermal Noise Microscopy

PubMed Central

Yao, Atsushi; Kobayashi, Kei; Nosaka, Shunta; Kimura, Kuniko; Yamada, Hirofumi

2017-01-01

Several researchers have recently demonstrated visualization of subsurface features with a nanometer-scale resolution using various imaging schemes based on atomic force microscopy. Since all these subsurface imaging techniques require excitation of the oscillation of the cantilever and/or sample surface, it has been difficult to identify a key imaging mechanism. Here we demonstrate visualization of Au nanoparticles buried 300 nm into a polymer matrix by measurement of the thermal noise spectrum of a microcantilever with a tip in contact to the polymer surface. We show that the subsurface Au nanoparticles are detected as the variation in the contact stiffness and damping reflecting the viscoelastic properties of the polymer surface. The variation in the contact stiffness well agrees with the effective stiffness of a simple one-dimensional model, which is consistent with the fact that the maximum depth range of the technique is far beyond the extent of the contact stress field. PMID:28210001

Effect of polymer residues on the electrical properties of large-area graphene–hexagonal boron nitride planar heterostructures

DOE PAGES

Voyloy, Dimitry; Lassiter, Matthew G.; Sokolov, Alexei P.; ...

2017-06-19

Polymer residue plays an important role in the performance of 2D heterostructured materials. Herein, we study the effect of polymer residual impurities on the electrical properties of graphene–boron nitride planar heterostructures. Large-area graphene (Gr) and hexagonal boron nitride (h-BN) monolayers were synthesized using chemical vapor deposition techniques. Atomic van-der-Waals heterostructure layers based on varied configurations of Gr and h-BN layers were assembled. The average interlayer resistance of the heterojunctions over a 1 cm 2 area for several planar heterostructure configurations was assessed by impedance spectroscopy and modeled by equivalent electrical circuits. As a result, conductive AFM measurements showed that themore » presence of polymer residues on the surface of the Gr and h-BN monolayers resulted in significant resistance deviations over nanoscale regions.« less

Effect of polymer residues on the electrical properties of large-area graphene–hexagonal boron nitride planar heterostructures

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

Voyloy, Dimitry; Lassiter, Matthew G.; Sokolov, Alexei P.

Polymer residue plays an important role in the performance of 2D heterostructured materials. Herein, we study the effect of polymer residual impurities on the electrical properties of graphene–boron nitride planar heterostructures. Large-area graphene (Gr) and hexagonal boron nitride (h-BN) monolayers were synthesized using chemical vapor deposition techniques. Atomic van-der-Waals heterostructure layers based on varied configurations of Gr and h-BN layers were assembled. The average interlayer resistance of the heterojunctions over a 1 cm 2 area for several planar heterostructure configurations was assessed by impedance spectroscopy and modeled by equivalent electrical circuits. As a result, conductive AFM measurements showed that themore » presence of polymer residues on the surface of the Gr and h-BN monolayers resulted in significant resistance deviations over nanoscale regions.« less

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.

Carboxymethylcellulose adsorption on molybdenite: the effect of electrolyte composition on adsorption, bubble-surface collisions, and flotation.

PubMed

Kor, Mohammad; Korczyk, Piotr M; Addai-Mensah, Jonas; Krasowska, Marta; Beattie, David A

2014-10-14

The adsorption of carboxymethylcellulose polymers on molybdenite was studied using spectroscopic ellipsometry and atomic force microscopy imaging with two polymers of differing degrees of carboxyl group substitution and at three different electrolyte conditions: 1 × 10(-2) M KCl, 2.76 × 10(-2) M KCl, and simulated flotation process water of multicomponent electrolyte content, with an ionic strength close to 2.76 × 10(-2) M. A higher degree of carboxyl substitution in the adsorbing polymer resulted in adsorbed layers that were thinner and with more patchy coverage; increasing the ionic strength of the electrolyte resulted in increased polymer layer thickness and coverage. The use of simulated process water resulted in the largest layer thickness and coverage for both polymers. The effect of the adsorbed polymer layer on bubble-particle attachment was studied with single bubble-surface collision experiments recorded with high-speed video capture and image processing and also with single mineral molybdenite flotation tests. The carboxymethylcellulose polymer with a lower degree of substitution resulted in almost complete prevention of wetting film rupture at the molybdenite surface under all electrolyte conditions. The polymer with a higher degree of substitution prevented rupture only when adsorbed from simulated process water. Molecular kinetic theory was used to quantify the effect of the polymer on the dewetting dynamics for collisions that resulted in wetting film rupture. Flotation experiments confirmed that adsorbed polymer layer properties, through their effect on the dynamics of bubble-particle attachment, are critical to predicting the effectiveness of polymers used to prevent mineral recovery in flotation.

PTFE-nanocomposites structure and wear-resistance changing in various methods of structural modification

NASA Astrophysics Data System (ADS)

Mashkov, Yu K.; Ruban, A. S.; Rogachev, E. A.; Chemisenko, O. V.

2018-01-01

Conditions of polymer materials usage containing nanoelements as modifiers significantly affect the requirements for their physic-mechanical and tribological properties. However, the mechanisms of nanoparticles effect to the polymers tribotechnical properties have not been studied enough. The article aim is to analyze the results of studying polytetrafluoroethylene modified with cryptocrystalline graphite and silicon dioxide and to determine the effectiveness of the modification methods used and methods for further improving filled PTFE mechanical and tribotechnical properties. The effect of modifiers to PCM supramolecular structure was analyzed with SEM methods. The results of modifying the PCM samples surface by depositing a copper film with ion-vacuum deposition methods and changing the structural-phase composition and tribological characteristics are considered. The findings make possible to characterize the physicochemical processes under frictional interaction in metal polymer tribosystems.

Effect of cellulose nanocrystals on crystallization kinetics of polycaprolactone

NASA Astrophysics Data System (ADS)

Migler, Kalman; Roy, Debjani; Kotula, Anthony; Natarajan, Bharath; Gilman, Jeffrey; Fox, Douglas

The development of biocompatible polymer composites that enhance mechanical properties while maintaining thermoplastic processability is a longstanding goal in sustainable materials. Here we compatibilize a crystallizable polymer and a nano-fiber via surface modification and study the properties and crystallization kinetics of the resulting composite. First we demonstrate that polycaprolactone (PCL) and cellulose nanocrystals (CNCs) can be well-compatibilized by replacing the Na+ of sulfated cellulose nanocrystals (Na-CNCs) with tertiary butyl ammonium cations and then melt mixing via twin-screw extrusion. Transmission electron microscope and high temperature melt rheology show that the modified CNCs were dispersed in the polymer matrix. We find the crystallization kinetics are substantially affected by the CNC as indicated by the simultaneous measures of modulus and conformational states; higher loadings of CNCs accelerated the kinetics. We further correlate the crystallization kinetics, mechanical properties and stability.

Evidence of a Transition Layer between the Free Surface and the Bulk.

PubMed

Ogieglo, Wojciech; Tempelman, Kristianne; Napolitano, Simone; Benes, Nieck E

2018-03-15

The free surface, a very thin layer at the interface between polymer and air, is considered the main source of the perturbations in the properties of ultrathin polymer films, i.e., nanoconfinement effects. The structural relaxation of such a layer is decoupled from the molecular dynamics of the bulk. The free surface is, in fact, able to stay liquid even below the temperature where the polymer resides in the glassy state. Importantly, this surface layer is expected to have a very sharp interface with the underlying bulk. Here, by analyzing the penetration of n-hexane into polystyrene films, we report on the existence of a transition region, not observed by previous investigations, extending for 12 nm below the free surface. The presence of such a layer permits reconciling the behavior of interfacial layers with current models and has profound implications on the performance of ultrathin membranes. We show that the expected increase in the flux of the permeating species is actually overruled by nanoconfinement.

Nanotribology of charged polymer brushes

NASA Astrophysics Data System (ADS)

Klein, Jacob

Polymers at surfaces, whose modern understanding may be traced back to early work by Sam Edwards1, have become a paradigm for modification of surface properties, both as steric stabilizers and as remarkable boundary lubricants2. Charged polymer brushes are of particular interest, with both technological implications and especially biological relevance where most macromolecules are charged. In the context of biolubrication, relevant in areas from dry eye syndrome to osteoarthritis, charged polymer surface phases and their complexes with other macromolecules may play a central role. The hydration lubrication paradigm, where tenaciously-held yet fluid hydration shells surrounding ions or zwitterions serve as highly-efficient friction-reducing elements, has been invoked to understand the excellent lubrication provided both by ionized3 and by zwitterionic4 brushes. In this talk we describe recent advances in our understanding of the nanotribology of such charged brush systems. We consider interactions between charged end-grafted polymers, and how one may disentangle the steric from the electrostatic surface forces5. We examine the limits of lubrication by ionized brushes, both synthetic and of biological origins, and how highly-hydrated zwitterionic chains may provide extremely effective boundary lubrication6. Finally we describe how the lubrication of articular cartilage in the major joints, a tribosystem presenting some of the greatest challenges and opportunities, may be understood in terms of a supramolecular synergy between charged surface-attached polymers and zwitterionic groups7. Work supported by European Research Council (HydrationLube), Israel Science Foundation (ISF), Petroleum Research Fund of the American Chemical Society, ISF-NSF China Joint Program.

Surface and Electrochemical Properties of Polymer Brush-Based Redox Poly(Ionic Liquid).

PubMed

Bui-Thi-Tuyet, Van; Trippé-Allard, Gaëlle; Ghilane, Jalal; Randriamahazaka, Hyacinthe

2016-10-26

Redox-active poly(ionic liquid) poly(3-(2-methacryloyloxy ethyl)-1-(N-(ferrocenylmethyl) imidazolium bis(trifluoromethylsulfonyl)imide deposited onto electrode surfaces has been prepared using surface-initiated atom transfer radical polymerization SI-ATRP. The process starts by electrochemical immobilization of initiator layer, and then methacrylate monomer carrying ferrocene and imidazolium units is polymerized in ionic liquid media via SI-ATRP process. The surfaces analyses of the polymer exhibit a well-defined polymer brushlike structure and confirm the presence of ferrocene and ionic moieties within the film. Furthermore, the electrochemical investigations of poly(redox-active ionic liquid) in different media demonstrate that the electron transfer is not restricted by the rate of counterion migration into/out of the polymer. The attractive electrochemical performance of these materials is further demonstrated by performing electrochemical measurement, of poly(ferrocene ionic liquid), in solvent-free electrolyte. The facile synthesis of such highly ordered electroactive materials based ionic liquid could be useful for the fabrication of nanostructured electrode suitable for performing electrochemistry in solvent free electrolyte. We also demonstrate possible applications of the poly(FcIL) as electrochemically reversible surface wettability system and as electrochemical sensor for the catalytic activity toward the oxidation of tyrosine.

Binary Polymer Brushes of Strongly Immiscible Polymers.

PubMed

Chu, Elza; Babar, Tashnia; Bruist, Michael F; Sidorenko, Alexander

2015-06-17

The phenomenon of microphase separation is an example of self-assembly in soft matter and has been observed in block copolymers (BCPs) and similar materials (i.e., supramolecular assemblies (SMAs) and homo/block copolymer blends (HBCs)). In this study, we use microphase separation to construct responsive polymer brushes that collapse to generate periodic surfaces. This is achieved by a chemical reaction between the minor block (10%, poly(4-vinylpyridine)) of the block copolymer and a substrate. The major block of polystyrene (PS) forms mosaic-like arrays of grafted patches that are 10-20 nm in size. Depending on the nature of the assembly (SMA, HBC, or neat BCP) and annealing method (exposure to vapors of different solvents or heating above the glass transition temperature), a range of "mosaic" brushes with different parameters can be obtained. Successive grafting of a secondary polymer (polyacrylamide, PAAm) results in the fabrication of binary polymer brushes (BPBs). Upon being exposed to specific selective solvents, BPBs may adopt different conformations. The surface tension and adhesion of the binary brush are governed by the polymer occupying the top stratum. The "mosaic" brush approach allows for a combination of strongly immiscible polymers in one brush. This facilitates substantial contrast in the surface properties upon switching, previously only possible for substrates composed of predetermined nanostructures. We also demonstrate a possible application of such PS/PAAm brushes in a tunable bioadhesion-bioadhesive (PS on top) or nonbioadhesive (PAAm on top) surface as revealed by Escherichia coli bacterial seeding.

Noncontact viscoelastic measurement of polymer thin films in a liquid medium using a long-needle AFM

NASA Astrophysics Data System (ADS)

Guan, Dongshi; Barraud, Chloe; Charlaix, Elisabeth; Tong, Penger

We report noncontact measurement of the viscoelastic property of polymer thin films in a liquid medium using frequency-modulation atomic force microscopy (FM-AFM) with a newly developed long-needle probe. The probe contains a long vertical glass fiber with one end adhered to a cantilever beam and the other end with a sharp tip placed near the liquid-film interface. The nanoscale flow generated by the resonant oscillation of the needle tip provides a precise hydrodynamic force acting on the soft surface of the thin film. By accurately measuring the mechanical response of the thin film, we obtain the elastic and loss moduli of the thin film using the linear response theory of elasto-hydrodynamics. The experiment verifies the theory and demonstrates its applications. The technique can be used to accurately measure the viscoelastic property of soft surfaces, such as those made of polymers, nano-bubbles, live cells and tissues. This work was supported by the Research Grants Council of Hong Kong SAR.

Poly(aryloxyphosphazenes) with Phenylphenoxy and Related Bulky Side Groups, Synthesis, Thermal Transition Behavior, and Optical Properties

DTIC Science & Technology

1989-06-09

revealed by differential scanning calorimetry. However, films of these polymers were not birefringent when viewed between crossed polarizers. Reports...C to 57*C. We intepret this to mean that the rigidity of the poly- mer and the intermolecular interactions are dominated by the one p-phenylphenoxy...of polymers 1-40 were measured at )-632nm using a modified critical angle method 32 (Figure 3). Films of the polymers were cast on one surface of a

Fabrication of polymer micro-lens array with pneumatically diaphragm-driven drop-on-demand inkjet technology.

PubMed

Xie, Dan; Zhang, Honghai; Shu, Xiayun; Xiao, Junfeng

2012-07-02

The paper reports an effective method to fabricate micro-lens arrays with the ultraviolet-curable polymer, using an original pneumatically diaphragm-driven drop-on-demand inkjet system. An array of plano convex micro-lenses can be formed on the glass substrate due to surface tension and hydrophobic effect. The micro-lens arrays have uniform focusing function, smooth and real planar surface. The fabrication process showed good repeatability as well, fifty micro-lenses randomly selected form 9 × 9 miro-lens array with an average diameter of 333.28μm showed 1.1% variations. Also, the focal length, the surface roughness and optical property of the fabricated micro-lenses are measured, analyzed and proved satisfactory. The technique shows great potential for fabricating polymer micro-lens arrays with high flexibility, simple technological process and low production cost.

Evaluation of flexural strength and surface properties of prepolymerized CAD/CAM PMMA-based polymers used for digital 3D complete dentures.

PubMed

Arslan, Mustafa; Murat, Sema; Alp, Gulce; Zaimoglu, Ali

2018-01-01

The objectives of this in vitro study were to evaluate the flexural strength (FS), surface roughness (Ra), and hydrophobicity of polymethylmethacrylate (PMMA)-based computer-aided design/computer-aided manufacturing (CAD/CAM) polymers and to compare the properties of different CAD/CAM PMMA-based polymers with conventional heat-polymerized PMMA following thermal cycling. Twenty rectangular-shaped specimens (64 × 10 × 3.3 mm) were fabricated from three CAD/CAM PMMA-based polymers (M-PM Disc [M], AvaDent Puck Disc [A], and Pink CAD/CAM Disc Polident [P], and one conventional heat-polymerized PMMA (Promolux [C]), according to ISO 20795-1:2013 standards. The specimens were divided into two subgroups (n = 10), a control and a thermocycled group. The specimens in the thermocycled group were subjected to 5000 thermal cycling procedures (5 to 55°C; 30 s dwell times). The Ra value was measured using a profilometer. Contact angle (CA) was assessed using the sessile drop method to evaluate surface hydrophobicity. In addition, the FS of the specimens was tested in a universal testing machine at a crosshead speed of 1.0 mm/min. Surface texture of the materials was assessed using scanning electron microscope (SEM). The data were analyzed using two-way analysis of variance (ANOVA), followed by Tukey's HSD post-hoc test (α < 0.05). CAD/CAM PMMA-based polymers showed significantly higher FS than conventional heat-polymerized PMMA for each group (P < 0.001). CAD/CAM PMMA-based polymer [P] showed the highest FS, whereas conventional PMMA [C] showed the lowest FS before and after thermal cycling (P < 0.001). There were no significant differences among the Ra values of the tested denture base polymers in the control group (P > 0.05). In the thermocycled group, the lowest Ra value was observed for CAD/CAM PMMA-based polymer [M] (P < 0.001), whereas CAD/CAM PMMA-based polymers [A] and [P], and conventional PMMA [C] had similar Ra values (P > 0.05). Conventional PMMA [C] had a significantly lower CA and consequently lower hydrophobicity compared to the CAD/CAM polymers in the control group (P < 0.001). In the thermocycled group, CAD/CAM PMMA-based polymer [A] and conventional PMMA [C] had significantly higher CA, and consequently higher hydrophobicity when compared to CAD/CAM polymers [M] and [P] (P < 0.001). However, no significant differences were found among the other materials (P > 0.05). The FS and hydrophobicity of the CAD/CAM PMMA-based polymers were higher than the conventional heat-polymerized PMMA, whereas the CAD/CAM PMMA-based polymers had similar Ra values to the conventional PMMA. Thermocycling had a significant effect on FS and hydrophobicity except for the Ra of denture base materials.

CuSO4/H2O2-Triggered Polydopamine/Poly(sulfobetaine methacrylate) Coatings for Antifouling Membrane Surfaces.

PubMed

Zhang, Chao; Li, Hao-Nan; Du, Yong; Ma, Meng-Qi; Xu, Zhi-Kang

2017-02-07

Mussel-inspired polydopamine (PDA) coatings have been broadly exploited for constructing functional membrane surfaces. One-step codeposition of PDA with antifouling polymers, especially zwitterionic polymers, has been regarded as a promising strategy for fabricating antifouling membrane surfaces. However, one challenge is that the codeposition is usually a slow process over 10 h or even several days. Herein, we report that CuSO 4 /H 2 O 2 is able to notably accelerate the codeposition process of PDA with poly(sulfobetaine methacrylate) (PSBMA). In our case, PSBMA is facilely anchored to the polypropylene microporous membrane (PPMM) surfaces within 1 h with the assistance of PDA because of its strong interfacial adhesion. The PDA/PSBMA-coated PPMMs show excellent surface hydrophilicity, high water permeation flux (7506 ± 528 L/m 2 ·h at 0.1 MPa), and an outstanding antifouling property. Moreover, the antifouling property is maintained after the membranes are treated with acid and alkali solutions as well as organic solvents. To recap, it provides a facile, universal, and time-saving strategy for exploiting high-efficiency and durable antifouling membrane surfaces.

Inhibition of the solid state transformation of carbamazepine in aqueous solution: impact of polymeric properties.

PubMed

Gift, Alan D; Hettenbaugh, Jacob A; Quandahl, Rachel A; Mapes, Madison

2017-11-06

The effects of polymers on the anhydrate-to-hydrate transformation of carbamazepine (CBZ) was investigated. The three types of polymers studied were polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA) and substituted celluloses which included hydroxypropyl methylcellulose (HPMC) and methylcellulose (MC). Anhydrous CBZ was added to dilute aqueous polymer solutions and Raman spectroscopy measurements were collected to monitor the kinetics of the solution-mediated transformation to CBZ dihydrate. Polymers exhibiting the greatest inhibition were able to reduce the growth phase of the solution-mediated transformation and change the habit of the hydrate crystal indicating polymer adsorption to the hydrate crystal surface as the mechanism of inhibition. The results of the various polymers showed that short chain substituted celluloses (HPMC and MC) inhibited the CBZ transformation to a much greater extent than longer chains. The same trend was observed for PVP and PVA, but to a lesser extent. These chain length effects were attributed to changes in polymer confirmation when adsorbed on the crystal surface. Additionally, decreasing the percentage of hydroxyl groups on the PVA polymer backbone reduced the ability of the polymer to inhibit the transformation and changing the degree of substitutions of methyl and hydroxypropyl groups on the cellulosic polymer backbone had no effect on the transformation.

Tube Visualization and Properties from Isoconfigurational Averaging

NASA Astrophysics Data System (ADS)

Qin, Jian; Bisbee, Windsor; Milner, Scott

2012-02-01

We introduce a simulation method to visualize the confining tube in polymer melts and measure its properties. We studied bead-spring ring polymers, which conveniently suppresses constraint release and contour length fluctuations. We allow molecules to cross and reach topologically equilibrated states by invoking various molecular rebridging moves in Monte Carlo simulations. To reveal the confining tube, we start with a well equilibrated configuration, turn off rebridging moves, and run molecular dynamics simulation multiple times, each with different initial velocities. The resulting set of ``movies'' of molecular trajectories defines an isoconfigurational ensemble, with the bead positions at different times and in different ``movies'' giving rise to a cloud. The cloud shows the shape, range and strength of the tube confinement, which enables us to study the statistical properties of tube. Using this approach, we studied the effects of free surface, and found that the tube diameter near the surface is greater than the bulk value by about 25%.

Mussel inspired polymerized P(TA-TETA) for facile functionalization of carbon nanotube

NASA Astrophysics Data System (ADS)

Si, Shuxian; Gao, Tingting; Wang, Junhao; Liu, Qinze; Zhou, Guowei

2018-03-01

This article describes a novel and effective approach for non-covalent modification of carbon nanotube (CNT) via the mussel inspired polymerization of tannic acid (TA) and triethylenetetramine (TETA) and subsequent surface initiated atom transfer radical polymerization (SI-ATRP). Fourier transform infrared spectroscopy (FT-IR), thermo-gravimetric analysis (TGA), transmission electron microscope (TEM), X-ray photoelectron spectroscopy (XPS) and photograph were used to study the successful preparation of polymer brush grafted CNT (CNT-P(TA-TETA)-PDMAEMA) composite as well as the pH-responsive behavior of the composite. Furthermore, by amine protonation and in situ reduction, gold nanoparticles were successfully uploaded and the catalytic property of CNT-P(TA-TETA)-PDMAEMA/Au was investigated. We believe that the surface functionalization strategy can be extended to graphene and other substrates, and the surface properties can be regulated by grafting polymer brushes with different functionalities.

Composite patterning devices for soft lithography

DOEpatents

Rogers, John A.; Menard, Etienne

2007-03-27

The present invention provides methods, devices and device components for fabricating patterns on substrate surfaces, particularly patterns comprising structures having microsized and/or nanosized features of selected lengths in one, two or three dimensions. The present invention provides composite patterning devices comprising a plurality of polymer layers each having selected mechanical properties, such as Young's Modulus and flexural rigidity, selected physical dimensions, such as thickness, surface area and relief pattern dimensions, and selected thermal properties, such as coefficients of thermal expansion, to provide high resolution patterning on a variety of substrate surfaces and surface morphologies.

Effect of TiO2 nanoparticles doping on structural and electrical properties of PVA: NaBr polymer electrolyte

NASA Astrophysics Data System (ADS)

Sagar, Rohan N.; Ravindrachary, V.; Guruswamy, B.; Hegde, Shreedatta; Mahanthesh, B. K.; Kumari, R. Padma

2018-05-01

The effect of TiO2 nanoparticles on morphology and electrical properties of PVA: NaBr composite films were carried out using various techniques. The pure and TiO2 nanoparticle doped PVA: NaBr composite films were prepared using solvent casting method. The FTIR spectral studies shows that the Ti+ ions of TiO2 interacts with hydroxyl group (OH) of PVA via hydrogen bonding and forms the charge transfer complexes (CTC). These interactions are of inter/intra molecular type and affects the surface morphology as well as the electrical properties of composite films. XRD study shows that the crystallinity of the composite increases with doping level. SEM studies shows that the increase in roughness of the surface of the composite films and uniform dispersion of nanofillers in polymer matrix. Electrical properties are analyzed using impedance analyzer and higher conductivity (10-4Scm-1) is achieved for 5 wt % TiO2 doping concentration.

PVD coating for optical applications on temperature-resistant thermoplastics

NASA Astrophysics Data System (ADS)

Munzert, Peter; Schulz, Ulrike; Kaiser, Norbert

2004-02-01

The performance of the high temperature resistant polymers Pleximid, APEC and Ultrason as substrate materials in plasma-assisted physical vapor deposition processes was studied and compared with well-known thermoplastics for optical applications. Different effects of UV irradiation and plasma exposure on the polymers' optical features, surface energy and adhesion properties for oxide layers, typically used for interference multilayer coatings, are shown.

Syntheses and properties of elastic copoly(ester-urethane)s containing a phospholipid moiety and the fabrication of nanosheets.

PubMed

Sirithep, Wariya; Morita, Kohei; Iwano, Atsushi; Komachi, Takuya; Okamura, Yosuke; Nagase, Yu

2014-01-01

In these years, we have investigated the syntheses of novel diamine and diol monomers containing phosphorylcholine (PC) group to obtain biocompatible polymers, the backbone components of which were thermally stable and mechanically strong. In this study, the preparations of elastic copoly(ester-urethane)s containing PC group and polycarbonate segment were carried out by polycondensation and polyaddition using a diol monomer containing PC group and polycarbonate diol. It was found that the obtained polymers exhibited the high-thermal stability up to 200 °C and the elasticity derived from the soft segment. The introduction of PC group was effective to improve the resistance to the adhesions of proteins and platelets on the polymer films, which was the result of surface properties derived from the PC moiety. In addition, we tried to prepare ultra-thin polymer films composed of copoly(ester-urethane)s, so-called nanosheets. As a result, the desired nanosheets were successfully fabricated and the obtained nanosheets exhibited the high adhesive strength, indicating that the nanosheets could conform closely to the desired surfaces due to their exquisite flexibility and low roughness.

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

Chaiko, David J.; Leyva, Argentina A.

The invention provides methods for making clay/wax nanocomposites and coatings and films of same with improved chemical resistance and gas barrier properties. The invention further provides methods for making and using emulsions of such clay/wax nanocomposites. Typically, an organophillic clay is combined with a wax or wax/polymer blend such that the cohesion energy of the clay matches that of the wax or wax/polymer blend. Suitable organophilic clays include mica and phyllosilicates that have been surface-treated with edge or edge and surface modifying agents. The resulting nanocomposites have applications as industrial coatings and in protective packaging.

Improvement of adhesion properties of low density polyethylene (LDPE) substrate using atmospheric plasma

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

Sanchez-Nacher, L.; Garcia-Sanoguera, D.; Fenollar, O.

2010-06-02

In this work we have used atmospheric plasma technology on polyethylene surface with different treatment conditions. These modify surface pre-treatments on polyethylene, thus having a positive effect on overall surface activity of polymer surface and, consequently, adhesion properties can be remarkably improved. We have evaluated the influence of the nozzle/substrate distance and atmospheric plasma speed on wettability changes and adhesion properties. Wettability changes have been studied by contact angle measurements and subsequent surface energy calculation. Mechanical characterization of adhesion joints has been carried out in two different ways: peel and shear tensile test. The overall results show a remarkable increasemore » in mechanical properties of adhesion joints for low nozzle/substrate distances and low speed. So plasma atmospheric technology is highly useful to increase adhesion properties of polypropylene.« less

Influence of substrate and film thickness on polymer LIPSS formation

NASA Astrophysics Data System (ADS)

Cui, Jing; Nogales, Aurora; Ezquerra, Tiberio A.; Rebollar, Esther

2017-02-01

Here we focus on the influence of both, substrate and film thickness on polymer Laser Induced Periodic Surface Structures (LIPSS) formation in polymer films. For this aim a morphological description of ripples structures generated on spin-coated polystyrene (PS) films by a linearly polarized laser beam with a wavelength of 266 nm is presented. The influence of different parameters on the quality and characteristics of the formed laser-induced periodic surface structures (LIPSS) was investigated. We found that well-ordered LIPSS are formed either on PS films thinner than 200 nm or thicker than 400 nm supported on silicon substrates as well as on thicker free standing films. However less-ordered ripples are formed on silicon supported films with intermediate thicknesses in the range of 200-380 nm. The effect of the thermal and optical properties of the substrate on the quality of LIPSS was analyzed. Differences observed in the fluence and number of pulses needed for the onset of surface morphological modifications is explained considering two main effects which are: (1) The temperature increase on polymer surface induced by the action of cumulative laser irradiation and (2) The differences in thermal conductivity between the polymer and the substrate which strongly affect the heat dissipation generated by irradiation.

Human monocyte adhesion and activation on crystalline polymers with different morphology and wettability in vitro.

PubMed

Young, T H; Lin, D T; Chen, L Y

2000-06-15

This study evaluated the effects of crystalline polyamide (Nylon-66), poly(ethylene-co-vinyl alcohol) (PEVA), and poly(vinylidene fluoride) (PVDF) polymers with nonporous and porous morphologies on the ability of monocytes to adhere and subsequently activate to produce IL-1beta, IL-6, and tumor necrosis factor alpha. The results indicated monocyte adhesion and activation on a material might differ to a great extent, depending on the surface morphology and wettability. As the polymer wettability increases, the ability of monocytes to adhere increases but the ability to produce cytokines decreases. Similarly, these polymers, when prepared with porous surfaces, enhance monocyte adhesion but suppress monocyte release of cytokines. Therefore, the hydrophobic PVDF with a nonporous surface stimulates the most activity in adherent monocytes but shows the greatest inhibition of monocyte adhesion when compared with all of the other membranes. In contrast, the hydrophilic Nylon-66, which has a porous surface, is a relatively better substrate for this work. Therefore, monocyte behavior on a biomaterial may be influenced by a specific surface property. Based on this result, we propose that monocyte adhesion is regulated by a different mechanism than monocyte activation. Consequently, the generation of cytokines by monocytes is not proportional to the number of cells adherent to the surface. Copyright 2000 John Wiley & Sons, Inc.

The influence of surface coating on the properties of water-soluble CdSe and CdSe/ZnS quantum dots

NASA Astrophysics Data System (ADS)

Coto-García, Ana María; Fernández-Argüelles, María T.; Costa-Fernández, José M.; Sanz-Medel, Alfredo; Valledor, Marta; Campo, Juan C.; Ferrero, Francisco J.

2013-01-01

It is well-known that ligands coating the surface of luminescent semiconductor nanocrystals (quantum dots [QDs]) play an important role in the preparation, stability and physical properties of the colloidal QDs in both organic and aqueous media. Here we report on the synthesis and characterization of core (CdSe QDs) and core-shell structured QDs (CdSe/ZnS QDs), both of them stabilized in aqueous medium through different mechanisms of modification of their surface chemistry. The approaches evaluated for QDs transfer to aqueous media were ligand exchange and polymer coating. Experiments were performed using two typical thioalkyl acids as ligands, namely mercaptoacetic acid (QDs-MAA) and 2-mercaptoethanesulphonic acid (QDs-MES), and an amphiphilic polymer (PQDs) based on poly(maleic anhydride) functional groups. The effects of pH (buffer solution), illumination and the presence of ions in the QD environment on the spectroscopic properties of the different synthesized QDs are reported. The stability of the prepared QDs has been comparatively evaluated aimed to elucidate which surface chemistry provides the suitable properties to be employed as fluorescence labels in distinct types of applications. The experimental results and conclusions will be useful for the development of sensitive sensors or assays adopting QDs as fluorescence labels.

Grafting of functionalized polymer on porous silicon surface using Grignard reagent

NASA Astrophysics Data System (ADS)

Tighilt, F.-Z.; Belhousse, S.; Sam, S.; Hamdani, K.; Lasmi, K.; Chazalviel, J. N.; Gabouze, N.

2017-11-01

Recently, considerable attention has been paid to the manipulation and the control of the physicochemical properties of porous silicon surfaces because of their crucial importance to the modern microelectronics industry. Hybrid structures consisting of deposited polymer on porous silicon surfaces are important to applications in microelectronics, photovoltaics and sensors (Ensafi et al., 2016; Kashyout et al., 2015; Osorio et al.; 2015; Hejjo et al., 2002) [1-4]. In many cases, the polymer can provide excellent mechanical and chemical protection of the substrate, changes the electrochemical interface characteristics of the substrate, and provides new ways to the functionalization of porous silicon surfaces for molecular recognition and sensing. In this work, porous silicon surface was modified by anodic treatment in ethynylmagnesium bromide electrolyte leading to the formation of a polymeric layer bearing some bromine substituents. Subsequently, the formed polymer is functionalized with amine molecules containing functional groups (carboxylic acid or pyridine) by a substitution reaction between bromine sites and amine groups (Hofmann reaction). The chemical composition of the modified porous silicon surfaces was investigated and the grafting of polymeric chains and functional groups on the porous silicon surface was confirmed by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) which displayed the principal characteristic peaks attributed to the different functional groups. Furthermore, the surface of the material was examined by scanning electron microscopy (SEM).

Design Concept of Dialyzer Biomaterials: How to Find Biocompatible Polymers Based on the Biointerfacial Water Structure.

PubMed

Tanaka, Masaru

2017-01-01

Although various types of materials have been used widely in dialyzers, most biomaterials lack the desired functional properties to interface with blood and have not been engineered for optimum performance. Therefore, there is increasing demand to develop novel materials to address such problems in the dialysis arena. Numerous parameters of polymeric biomaterials can affect biocompatibility in a controlled manner. The mechanisms responsible for the biocompatibility of polymers at the molecular level have not been clearly demonstrated, although many theoretical and experimental efforts have been made to try and understand them. Moreover, water interactions have been recognized as fundamental for the blood response to contact with polymers. We have proposed the 'intermediate water' concept and hypothesized that intermediate water, which prevents the proteins and blood cells from directly contacting the polymer surface, or nonfreezing water on the polymer surface, plays an important role in the biocompatibility of polymers. This chapter provides an overview of the recent experimental progress of biocompatible polymers measured by thermal, spectroscopic, and surface force techniques. Additionally, it highlights recent developments in the use of biocompatible polymeric biomaterials for dialyzers and provides an overview of the progress made in the design of multifunctional biomedical polymers by controlling the biointerfacial water structure through precision polymer synthesis. Key Messages: Intermediate water was found only in hydrated biopolymers (proteins, polysaccharides, and nucleic acids, DNA and RNA) and hydrated biocompatible synthetic polymers. Intermediate water could be one of the main screening factors for the design of appropriate dialyzer materials. © 2017 S. Karger AG, Basel.

Chemically Modified Polyvinyl Chloride for Removal of Thionine Dye (Lauth’s Violet)

PubMed Central

Silva, Cleuzilene V.; Royer, Betina; Rodrigues Filho, Guimes; Cerqueira, Daniel A.; Assunção, Rosana M. N.

2017-01-01

The chemical modification of hydrophobic polymer matrices is an alternative way to elchange their surface properties. The introduction of sulfonic groups in the polymer changes the surface properties such as adhesion, wettability, catalytic ability, and adsorption capacity. This work describes the production and application of chemically modified polyvinyl chloride (PVC) as adsorbent for dyes removal. Chemical modification of PVC was evaluated by infrared spectroscopy and elemental analysis, which indicated the presence of sulfonic groups on PVC. The chemically modified PVC (PVCDS) showed an ion exchange capacity of 1.03 mmol−1, and efficiently removed the thionine dye (Lauth’s violet) from aqueous solutions, reaching equilibrium in 30 min. The adsorption kinetics was better adjusted for a pseudo second order model. This result indicates that the adsorption of thionine onto PVCDS occurs by chemisorption. Among the models for the state of equilibrium, SIPS and Langmuir exhibited the best fit to the experimental results and PVCDS showed high adsorption capacities (370 mg−1). Thus, it is assumed that the system presents homogeneous characteristics to the distribution of active sites. The modification promoted the formation of surface characteristics favorable to the dye adsorption by the polymer. PMID:29137158

Polymer Mixtures and Films: Free Volume as a Driving Force for Miscibility and Glassiness

NASA Astrophysics Data System (ADS)

DeFelice, Jeffrey

The microscopic characteristics of polymer molecules are connected with many macro- scopic and mechanical properties of their liquid (pure or mixed) and solid states. How these properties are affected by the different molecular attributes of polymers is of particular interest for practical applications of polymer materials. In Part I of this thesis, the thermodynamics of polymer/supercritical CO2 mixtures and blends of linear and branched polymers are modeled using a lattice based equation of state approach. Analyses of trends in the pure component physical properties lead to insight regarding how changes in molecular architecture and/or isotopic labeling affect the relative compatibilities of the mixtures. This approach is also applied to the mixed state to predict the enthalpic and entropic changes of mixing, from which, information is provided about the role of pure component properties in controlling the underlying thermodynamics of the mixtures. In Part II, the focus of this thesis turns to how interfacial effects can shift a number of physical properties in glass forming fluids relative to those of the pure bulk material. One of the most notable deviations from bulk behavior that has been reported for these systems is a change in the glass transition temperature (Tg). In this work, interfacial effects on Tg are probed in film and polymer/additive systems using a simple kinetic lattice model that simulates free volume and mobility in glass forming fluids. For films, the thickness-dependent behavior of Tg is characterized for different types of interfaces, including films that are substrate supported, free- standing, and 'stacked'. Connections are drawn between the size of the region of enhanced mobility near a free surface and the distribution of local Tg values across a film. For polymer/additive systems, where the "interface" is dispersed throughout the material, trends in additive induced Tg changes are analyzed with respect to additive concentration and the strength of the additive's influence on the local mobility of the polymer matrix.

Self-assembly of conjugated oligomers and polymers at the interface: structure and properties.

PubMed

Xu, Lirong; Yang, Liu; Lei, Shengbin

2012-08-07

In this review, we give a brief account on the recent scanning tunneling microscopy investigation of interfacial structures and properties of π-conjugated semiconducting oligomers and polymers, either at the solid-air (including solid-vacuum) or at the solid-liquid interface. The structural aspects of the self-assembly of both oligomers and polymers are highlighted. Conjugated oligomers can form well ordered supramolecular assemblies either at the air-solid or liquid-solid interface, thanks to the relatively high mobility and structural uniformity in comparison with polymers. The backbone structure, substitution of side chains and functional groups can affect the assembling behavior significantly, which offers the opportunity to tune the supramolecular structure of these conjugated oligomers at the interface. For conjugated polymers, the large molecular weight limits the mobility on the surface and the distribution in size also prevents the formation of long range ordered supramolecular assembly. The submolecular resolution obtained on the assembling monolayers enables a detailed investigation of the chain folding at the interface, both the structural details and the effect on electronic properties. Besides the ability in studying the assembling structures at the interfaces, STM also provides a reasonable way to evaluate the distribution of the molecular weight of conjugated polymers by statistic of the contour length of the adsorbed polymer chains. Both conjugated oligomers and polymers can form composite assemblies with other materials. The ordered assembly of oligomers can act as a template to controllably disperse other molecules such as coronene or fullerene. These investigations open a new avenue to fine tune the assembling structure at the interface and in turn the properties of the composite materials. To summarize scanning tunneling microscopy has demonstrated its surprising ability in the investigation of the assembling structures and properties of conjugated oligomers and polymers. The information obtained could benefit the understanding of the elements affecting the film morphology and helps the optimization of device performance.

Atomic Force Microscopy: A Powerful Tool to Address Scaffold Design in Tissue Engineering.

PubMed

Marrese, Marica; Guarino, Vincenzo; Ambrosio, Luigi

2017-02-13

Functional polymers currently represent a basic component of a large range of biological and biomedical applications including molecular release, tissue engineering, bio-sensing and medical imaging. Advancements in these fields are driven by the use of a wide set of biodegradable polymers with controlled physical and bio-interactive properties. In this context, microscopy techniques such as Atomic Force Microscopy (AFM) are emerging as fundamental tools to deeply investigate morphology and structural properties at micro and sub-micrometric scale, in order to evaluate the in time relationship between physicochemical properties of biomaterials and biological response. In particular, AFM is not only a mere tool for screening surface topography, but may offer a significant contribution to understand surface and interface properties, thus concurring to the optimization of biomaterials performance, processes, physical and chemical properties at the micro and nanoscale. This is possible by capitalizing the recent discoveries in nanotechnologies applied to soft matter such as atomic force spectroscopy to measure surface forces through force curves. By tip-sample local interactions, several information can be collected such as elasticity, viscoelasticity, surface charge densities and wettability. This paper overviews recent developments in AFM technology and imaging techniques by remarking differences in operational modes, the implementation of advanced tools and their current application in biomaterials science, in terms of characterization of polymeric devices in different forms (i.e., fibres, films or particles).

The Effects of Polymer Carrier, Hot Melt Extrusion Process and Downstream Processing Parameters on the Moisture Sorption Properties of Amorphous Solid Dispersions

PubMed Central

Feng, Xin; Vo, Anh; Patil, Hemlata; Tiwari, Roshan V.; Alshetaili, Abdullah S.; Pimparade, Manjeet B.; Repka, Michael A.

2017-01-01

Objective The aim of this study was to evaluate the effect of polymer carrier, hot melt extrusion (HME) and downstream processing parameters on the water uptake properties of amorphous solid dispersions. Methods Three polymers and a model drug were used to prepare amorphous solid dispersions utilizing HME technology. The sorption-desorption isotherms of solid dispersions and their physical mixtures were measured by the Dynamic Vapor Sorption system, and the effect of polymer hydrophobicity, hygroscopicity, molecular weight and the HME process were investigated. FTIR imaging was performed to understand the phase separation driven by the moisture. Key findings Solid dispersions with polymeric carriers with lower hydrophilicity, hygroscopicity, and higher molecular weight could sorb less moisture under the high RH conditions. The water uptake ability of polymer-drug solid dispersion systems were decreased compared to the physical mixture after HME, which might be due to the decreased surface area and porosity. The FTIR imaging indicated the homogeneity of the drug molecularly dispersed within the polymer matrix was changed after exposure to high RH. Conclusion Understanding the effect of formulation and processing on the moisture sorption properties of solid dispersions is essential for the development of drug products with desired physical and chemical stability. PMID:26589107

Molecular Design of Antifouling Polymer Brushes Using Sequence-Specific Peptoids

DOE PAGES

Lau, King Hang Aaron; Sileika, Tadas S.; Park, Sung Hyun; ...

2014-11-26

Material systems that can be used to flexibly and precisely define the chemical nature and molecular arrangement of a surface would be invaluable for the control of complex biointerfacial interactions. For example, progress in antifouling polymer biointerfaces that prevents nonspecific protein adsorption and cell attachment, which can significantly improve the performance of an array of biomedical and industrial applications, is hampered by a lack of chemical models to identify the molecular features conferring their properties. Poly(N-substituted glycine) “peptoids” are peptidomimetic polymers that can be conveniently synthesized with specific monomer sequences and chain lengths, and are presented as a versatile platformmore » for investigating the molecular design of antifouling polymer brushes. Zwitterionic antifouling polymer brushes have captured significant recent attention, and a targeted library of zwitterionic peptoid brushes with different charge densities, hydration, separations between charged groups, chain lengths, and grafted chain densities, is quantitatively evaluated for their antifouling properties through a range of protein adsorption and cell attachment assays. Specific zwitterionic brush designs are found to give rise to distinct but subtle differences in properties. In conclusion, the results also point to the dominant roles of the grafted chain density and chain length in determining the performance of antifouling polymer brushes.« less

Functional lignocellulosic materials prepared by ATRP from a wood scaffold.

PubMed

Cabane, Etienne; Keplinger, Tobias; Künniger, Tina; Merk, Vivian; Burgert, Ingo

2016-08-10

Wood, a natural and abundant source of organic polymers, has been used as a scaffold to develop novel wood-polymer hybrid materials. Through a two-step surface-initiated Atom Transfer Radical Polymerization (ATRP), the porous wood structure can be effectively modified with polymer chains of various nature. In the present study, polystyrene and poly(N-isopropylacrylamide) were used. As shown with various characterization techniques including confocal Raman microscopy, FTIR, and SEM/EDX, the native wood ultrastructure and features are retained and the polymer chains can be introduced deep within the wood, i.e. inside the wood cell walls. The physical properties of the new materials have been studied, and results indicate that the insertion of polymer chains inside the wood cell wall alters the intrinsic properties of wood to yield a hybrid composite material with new functionalities. This approach to the functionalization of wood could lead to the fabrication of a new class of interesting functional materials and promote innovative utilizations of the renewable resource wood.

Functional lignocellulosic materials prepared by ATRP from a wood scaffold

PubMed Central

Cabane, Etienne; Keplinger, Tobias; Künniger, Tina; Merk, Vivian; Burgert, Ingo

2016-01-01

Wood, a natural and abundant source of organic polymers, has been used as a scaffold to develop novel wood-polymer hybrid materials. Through a two-step surface-initiated Atom Transfer Radical Polymerization (ATRP), the porous wood structure can be effectively modified with polymer chains of various nature. In the present study, polystyrene and poly(N-isopropylacrylamide) were used. As shown with various characterization techniques including confocal Raman microscopy, FTIR, and SEM/EDX, the native wood ultrastructure and features are retained and the polymer chains can be introduced deep within the wood, i.e. inside the wood cell walls. The physical properties of the new materials have been studied, and results indicate that the insertion of polymer chains inside the wood cell wall alters the intrinsic properties of wood to yield a hybrid composite material with new functionalities. This approach to the functionalization of wood could lead to the fabrication of a new class of interesting functional materials and promote innovative utilizations of the renewable resource wood. PMID:27506369

The sorption properties of polymers with molecular imprints of chlorine-containing pesticides

NASA Astrophysics Data System (ADS)

Popov, S. A.; Dmitrienko, S. G.; Chumichkina, Yu. A.; Zolotov, Yu. A.

2009-04-01

Polymers with molecular imprints of 2,4-dichlorophenoxyacetic acid (2,4-D), 3,6-dichloro-2-methoxybenzoic acid (dicamba), and (RS)-1- p-chlorophenyl-4,4-dimethyl-3-(1H-1,2,4-triazol-1-ylmethyl) pentan-3-ol and the corresponding blank polymers were synthesized using acrylamide as a functional monomer. The specific surface area of the resulting materials was estimated and their sorption properties were studied. It was found that the sorption characteristics of the polymers with molecular imprints of chlorine-containing pesticides depended on the nature of template molecules, functional monomer: template ratio in the polymerization mixture, and nature and content of solvents varied at the synthesis stage. According to the sorption isotherms, the difference in the sorption behavior of molecularly imprinted and blank polymers was observed over a wide range of chlorine-containing pesticide concentrations. The selectivity of the adsorbent with 2,4-D imprints was estimated for the example of structurally related compounds.

Current Trends in Sensors Based on Conducting Polymer Nanomaterials

PubMed Central

Yoon, Hyeonseok

2013-01-01

Conducting polymers represent an important class of functional organic materials for next-generation electronic and optical devices. Advances in nanotechnology allow for the fabrication of various conducting polymer nanomaterials through synthesis methods such as solid-phase template synthesis, molecular template synthesis, and template-free synthesis. Nanostructured conducting polymers featuring high surface area, small dimensions, and unique physical properties have been widely used to build various sensor devices. Many remarkable examples have been reported over the past decade. The enhanced sensitivity of conducting polymer nanomaterials toward various chemical/biological species and external stimuli has made them ideal candidates for incorporation into the design of sensors. However, the selectivity and stability still leave room for improvement. PMID:28348348

Durable anti-fogging effect and adhesion improvement on polymer surfaces

NASA Astrophysics Data System (ADS)

Moser, E. M.; Gilliéron, D.; Henrion, G.

2010-01-01

The hydrophobic properties of polymeric surfaces may cause fogging in transparent packaging and poor adhesion to printing colours and coatings. Novel plasma processes for durable functionalization of polypropylene and polyethylene terephthalate substrates were developed and analysed using optical emission spectroscopy. A worm-like nano pattern was created on the polypropylene surface prior to the deposition of thin polar plasma polymerised layers. For both substrates, highly polar surfaces exhibiting a surface tension of up to 69 mN/m and a water contact angle of about 10° were produced - providing the anti-fogging effect. The deposition of thin plasma polymerised layers protects the increased surface areas and enables to tailoring the surface energy of the substrate in a wide range. Wetting characteristics were determined by dynamic contact angle measurements. Investigations of the chemical composition of several layers using X-ray photoelectron spectroscopy and FT-infrared spectroscopy were correlated with functional testing. The surface topography was investigated using atomic force microscopy. The weldability and peeling-off characteristics of the plasma treated polymer films could be adjusted by varying the process parameters. Global and specific migration analyses were undertaken in order to ensure the manufacturing of plasma treated polymer surfaces for direct food contact purposes.

Fabrication and Characterization of Conductive Conjugated Polymer-Coated Antheraea mylitta Silk Fibroin Fibers for Biomedical Applications.

PubMed

Gh, Darshan; Kong, Dexu; Gautrot, Julien; Vootla, Shyam Kumar

2017-07-01

Conductive polymers are interesting materials for a number of biological and medical applications requiring electrical stimulation of cells or tissues. Highly conductive polymers (polypyrrole and polyaniline)/Antheraea mylitta silk fibroin coated fibers are fabricated successfully by in situ polymerization without any modification of the native silk fibroin. Coated fibers characterized by scanning electron microscopy confirm the silk fiber surface is covered by conductive polymers. Thermogravimetric analysis reveals preserved thermal stability of silk fiber after coating process. X-ray diffraction of degummed fiber diffraction peaks at around 2θ = 20.4 and 16.5 confirms the preservation of the β-sheet structure typical of degummed silk II fibers. This phenomenon implies that both polypyrrole and polyaniline chains form interactions with peptide linkages in degummed fiber macromolecules, without significantly disrupting protein assembly. Fourier transform infrared spectroscopy of coated fibers indicates hydrogen bonding and electrostatic interactions exist between silk fibroin macromolecules and conductive polymers. Resulting fibers display good conductive properties compared to corresponding conjugated polymers. In vitro analysis (live/dead assay) of the behavior of human immortalized keratinocytes (HaCaTs) on coated fibers demonstrates improved cell-adhesive properties and viability after polymers coating. Hence, polypyrrole- and polyaniline-coated A. mylitta silk fibers are suitable for application in cell culture and for tissue engineering, where electrical conduction properties are required. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design and development of low cost polyurethane biopolymer based on castor oil and glycerol for biomedical applications.

PubMed

Tan, A C W; Polo-Cambronell, B J; Provaggi, E; Ardila-Suárez, C; Ramirez-Caballero, G E; Baldovino-Medrano, V G; Kalaskar, D M

2018-02-01

In the current study, we present the synthesis of novel low cost bio-polyurethane compositions with variable mechanical properties based on castor oil and glycerol for biomedical applications. A detailed investigation of the physicochemical properties of the polymer was carried out by using mechanical testing, ATR-FTIR, and X-ray photoelectron spectroscopy (XPS). Polymers were also tested in short term in-vitro cell culture with human mesenchymal stem cells to evaluate their biocompatibility for potential applications as biomaterial. FTIR analysis confirmed the synthesis of castor oil and glycerol based PU polymers. FTIR also showed that the addition of glycerol as co-polyol increases crosslinking within the polymer backbone hence enhancing the bulk mechanical properties of the polymer. XPS data showed that glycerol incorporation leads to an enrichment of oxidized organic species on the surface of the polymers. Preliminary investigation into in vitro biocompatibility showed that serum protein adsorption can be controlled by varying the glycerol content with polymer backbone. An alamar blue assay looking at the metabolic activity of the cells indicated that castor oil based PU and its variants containing glycerol are non-toxic to the cells. This study opens an avenue for using low cost bio-polyurethane based on castor oil and glycerol for biomedical applications. © 2017 The Authors Biopolymers Published by Wiley Periodicals, Inc.

Soft contact lens biomaterials from bioinspired phospholipid polymers.

PubMed

Goda, Tatsuro; Ishihara, Kazuhiko

2006-03-01

Soft contact lens (SCL) biomaterials originated from the discovery of a poly(2-hydroxyethyl methacrylate) (poly[HEMA])-based hydrogel in 1960. Incorporation of hydrophilic polymers into poly(HEMA) hydrogels was performed in the 1970-1980s, which brought an increase in the equilibrium water content, leading to an enhancement of the oxygen permeability. Nowadays, the poly(HEMA)-based hydrogels have been applied in disposable SCL. At the same time, high oxygen-permeable silicone hydrogels were produced, which made it possible to continually wear SCL. Recently, numerous trials for improving the water wettability of silicone hydrogels have been performed. However, little attention has been paid to improving their anti-biofouling properties and biocompatibility. Since biomimetic phospholipid polymers possess excellent anti-biofouling properties and biocompatibility they have the potential to play a valuable role in the surface modification of the silicone hydrogel. The representative phospholipid polymers containing a 2-methacryloyloxyethyl phosphorylcholine (MPC) unit suppressed nonspecific protein adsorption, increased cell compatibility and contributed to blood compatible biomaterials. The MPC polymer coating on the silicone hydrogel improved its water wettability and biocompatibility, while maintaining high oxygen permeability compared with the original silicone hydrogel. Furthermore, the newly prepared phospholipid-type intermolecular crosslinker made it possible to synthesize a 100% phospholipid polymer hydrogel that can enhance the anti-biofouling properties and biocompatibility. In this review, the authors discuss how polymer hydrogels should be designed in order to obtain a biocompatible SCL and future perspectives.

Direct Fabrication of Inkjet-Printed Dielectric Film for Metal-Insulator-Metal Capacitors

NASA Astrophysics Data System (ADS)

Cho, Cheng-Lin; Kao, Hsuan-ling; Wu, Yung-Hsien; Chang, Li-Chun; Cheng, Chun-Hu

2018-01-01

In this study, an inkjet-printed dielectric film that used a polymer-based SU-8 ink was fabricated for use in a metal-insulator-metal (MIM) capacitor. Thermal treatment of the inkjet-printed SU-8 polymer film affected its surface morphology, chemical structure, and surface wettability. A 20-min soft-bake at 60°C was applied to eliminate inkjet-printed bubbles and ripples. The ultraviolet-exposed SU-8 polymer film was crosslinked at temperatures between 120°C and 220°C and became disordered at 270°C, demonstrated using Fourier-transform infrared spectroscopy. A maximum SU-8 polymer film hard-bake temperature of 120°C was identified, and a printing process was subsequently employed because the appropriate water contact angle of the printed film was 79°. Under the appropriate inkjet printing conditions, the two-transmission-line method was used to extract the dielectric and electrical properties of the SU-8 polymer film, and the electrical behavior of the fabricated MIM capacitor was also characterized.

Space environment effects on polymers in low earth orbit

NASA Astrophysics Data System (ADS)

Grossman, E.; Gouzman, I.

2003-08-01

Polymers are widely used in space vehicles and systems as structural materials, thermal blankets, thermal control coatings, conformal coatings, adhesives, lubricants, etc. The low earth orbit (LEO) space environment includes hazards such as atomic oxygen, UV radiation, ionizing radiation (electrons, protons), high vacuum, plasma, micrometeoroids and debris, as well as severe temperature cycles. Exposure of polymers and composites to the space environment may result in different detrimental effects via modification of their chemical, electrical, thermal, optical and mechanical properties as well as surface erosion. The high vacuum induces material outgassing (e.g. low-molecular weight residues, plasticizers and additives) and consequent contamination of nearby surfaces. The present work reviews the LEO space environment constituents and their interactions with polymers. Examples of degradation of materials exposed in ground simulation facilities are presented. The issues discussed include the erosion mechanisms of polymers, formation of contaminants and their interaction with the space environment, and protection of materials from the harsh space environment.

Evaluation of dose dependent antimicrobial activity of self-assembled chitosan, nano silver and chitosan-nano silver composite against several pathogens.

PubMed

Tareq, Foysal Kabir; Fayzunnesa, Mst; Kabir, Md Shahariar; Nuzat, Musrat

2018-01-01

The aim of this investigation to preparation of silver nanoparticles organized chitosan nano polymer, which effective against microbial and pathogens, when apply to liquid medium and edible food products surface, will rescue the growth of microbes. Self-assembly approach used to synthesis of silver nanoparticles and silver nanoparticles organized chitosan nano polymer. Silver nanoparticles and silver nanoparticles organized chitosan nano polymer and film characterized using Ultra-violate visible spectrometer (UV-vis), X-ray diffraction (X-ray), and Scanning electronic microscope (SEM). The crystalline structured protein capped nano silver successfully synthesized at range of 12 nm-29 nm and organized into chitosan nano polymer. Antimicrobial ingredient in liquid medium and food product surface provide to rescue oxidative change and growth of microorganism to provide higher safety. The silver nanoparticles organized chitosan nano polymer caused the death of microorganism. The materials in nano scale synthesized successfully using self-assembly method, which showed good antimicrobial properties. Copyright © 2017 Elsevier Ltd. All rights reserved.

The effect of oxyalkylation and application of polymer dispersions on the thermoformability and extensibility of paper.

PubMed

Kouko, Jarmo; Setälä, Harri; Tanaka, Atsushi; Khakalo, Alexey; Ropponen, Jarmo; Retulainen, Elias

2018-04-15

Wood fiber-based packaging materials, as renewable materials, have growing market potential due to their sustainability. A new breakthrough in cellulose-based packaging requires some improvement in the mechanical properties of paper. Bleached softwood kraft pulp was mechanically treated, in two stages, using high- and low-consistency refining, sequentially. Chemical treatment of pulp using the oxyalkylation method was applied to modify a portion of fiber material, especially the fiber surface, and its compatibility with polymer dispersions including one carbohydrate polymer. The results showed that the compatibility of the cellulosic fibers with some polymers could be improved with oxyalkylation. By adjusting mechanical and chemical treatments, and the thermoforming conditions, the formability of paper was improved, but simultaneously the strength and stiffness decreased. The results suggest that the formability of the paper is not a direct function of the extensibility of the applied polymer, but also depends on the fiber network structure and surface energy. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

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

Cai, Chang-Yun; Yang, Hongta, E-mail: hyang@dragon.nchu.edu.tw; Lin, Kun-Yi Andrew

This article reports a scalable technology for fabricating polymer films with excellent water-repelling and anti-ultraviolet properties. A roll-to-roll compatible doctor blade coating technology is utilized to prepare silica colloidal crystal-polymer composites. The silica microspheres can then be selectively removed to create flexible self-standing macroporous polymer films with crystalline arrays of pores. The void sizes are controlled by tuning the duration of a reactive ion etching process prior to the removal of the templating silica microspheres. After surface modification, superhydrophobic surface can be achieved. This study further demonstrates that the as-prepared transparent porous films with 200 nm of pores exhibit diffraction ofmore » ultraviolet lights originated from the Bragg's diffractive of light from the three-dimensional highly ordered air cavities.« less

Carbon Redox-Polymer-Gel Hybrid Supercapacitors.

PubMed

Vlad, A; Singh, N; Melinte, S; Gohy, J-F; Ajayan, P M

2016-02-26

Energy storage devices that provide high specific power without compromising on specific energy are highly desirable for many electric-powered applications. Here, we demonstrate that polymer organic radical gel materials support fast bulk-redox charge storage, commensurate to surface double layer ion exchange at carbon electrodes. When integrated with a carbon-based electrical double layer capacitor, nearly ideal electrode properties such as high electrical and ionic conductivity, fast bulk redox and surface charge storage as well as excellent cycling stability are attained. Such hybrid carbon redox-polymer-gel electrodes support unprecedented discharge rate of 1,000C with 50% of the nominal capacity delivered in less than 2 seconds. Devices made with such electrodes hold the potential for battery-scale energy storage while attaining supercapacitor-like power performances.

Nanoscaled surface patterning of conducting polymers.

PubMed

Jiang, Lin; Wang, Xing; Chi, Lifeng

2011-05-23

In continuing the steady development of integrated-circuit-related fabrication, the ability to pattern conducting polymers into smaller and smaller sizes in order to realize devices with enhanced performance or even wholly new properties begins to take a more prominent role in their advanced applications. This review summarizes the recent advances in top-down and bottom-up patterning of conducting polymers on surfaces with different approaches including direct writing, in-situ synthesis or assembly, etching, and nanoscratching. All of the latest emerging strategies have the potential to go beyond the current state of the art towards real progress in terms of high-precision positioning, high resolution, high throughout, higher stability, facile processing, and lower-cost production. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Insight into Flufenamic Acid Cocrystal Dissolution in the Presence of a Polymer in Solution: from Single Crystal to Powder Dissolution.

PubMed

Guo, Minshan; Wang, Ke; Qiao, Ning; Fábián, László; Sadiq, Ghazala; Li, Mingzhong

2017-12-04

Effects of three polymers, polyethylene glycol (PEG), polyvinylpyrrolidone (PVP), and copolymer of vinylpyrrolidone/vinyl acetate (PVP-VA), on the dissolution behavior of the cocrystals of flufenamic acid with theophylline (FFA-TP CO) and nicotinamide (FFA-NIC CO) were investigated at multiple length scales. At the molecular level, the interactions of crystal surfaces with a polymer were analyzed by observing etching pattern changes using atomic force microscopy. At the macroscopic scale, dissolution rates of particular faces of a single crystal were determined by measurement of the physical retreat velocities of the faces using optical light microscopy. In the bulk experiments, the FFA concentration in a dissolution medium in the absence or presence of a polymer was measured under both sink and nonsink conditions. It has been found that the dissolution mechanisms of FFA-TP CO are controlled by the defect sites of the crystal surface and by precipitation of the parent drug FFA as individual crystals in the bulk fluid. In contrast, the dissolution mechanisms of FFA-NIC CO are controlled by surface layer removal and by a surface precipitation mechanism, where the parent drug FFA precipitates directly onto the surface of the dissolving cocrystals. Through controlling the dissolution environment by predissolving a polymer, PVP or PVP-VA, which can interact with the crystal surface to alter its dissolution properties, improved solubility, and dissolution rates of FFA-TP CO and FFA-NIC CO have been demonstrated.

The surface properties of fluorinated polyimides exposed to VUV and atomic oxygen

NASA Technical Reports Server (NTRS)

Forsythe, John S.; George, Graeme A.; Hill, David J. T.; Odonnell, James H.; Pomery, Peter J.; Rasoul, Firas A.

1995-01-01

The effect of atomic oxygen flux and VUV radiation alone and in combination on the surface of fluorinated polyimide films was studied using XPS spectroscopy. Exposure of fluorinated polyimides to VUV radiation alone caused no observable damage to the polymer surface, while an atomic oxygen flux resulted in substantial oxidation of the surface. On the other hand, exposure to VUV radiation and atomic oxygen in combination caused extensive oxidation of the polymer surface after only 2 minutes of exposure. The amount of oxidized carbon on the polymer surface indicated that there is aromatic ring opening oxidation. The changes in the O1s/C1s, N1s/C1s, and F1s/C1s ratios suggested that an ablative degradation process is highly favorable. A synergistic effect of VUV radiation in the presence of atomic oxygen is clearly evidenced from the XPS study. The atomic oxygen could be considered as the main factor in the degradation process of fluorinated polyimide films exposed to a low earth orbit environment.

Nanostructured Conjugated Polymers for Energy-Related Applications beyond Solar Cells.

PubMed

Xie, Jian; Zhao, Cui-E; Lin, Zong-Qiong; Gu, Pei-Yang; Zhang, Qichun

2016-05-20

To meet the ever-increasing requirements for the next generation of sustainable and versatile energy-related devices, conjugated polymers, which have potential advantages over small molecules and inorganic materials, are among the most promising types of green candidates. The properties of conjugated polymers can be tuned through modification of the structure and incorporation of different functional moieties. In addition, superior performances can be achieved as a result of the advantages of nanostructures, such as their large surface areas and the shortened pathways for charge transfer. Therefore, nanostructured conjugated polymers with different properties can be obtained to be applied in different energy-related organic devices. This review focuses on the application and performance of the recently reported nanostructured conjugated polymers for high-performance devices, including rechargeable lithium batteries, microbial fuel cells (MFCs), thermoelectric generators, and photocatalytic systems. The design strategies, reaction mechanisms, advantages, and limitations of nanostructured conjugated polymers are further discussed in each section. Finally, possible routes to improve the performances of the current systems are also included in the conclusion. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fiber lubrication: A molecular dynamics simulation study

NASA Astrophysics Data System (ADS)

Liu, Hongyi

Molecular and mesoscopic level description of friction and lubrication remains a challenge because of difficulties in the phenomenological understanding of to the behaviors of solid-liquid interfaces during sliding. Fortunately, there is the computational simulation approach opens an opportunity to predict and analyze interfacial phenomena, which were studied with molecular dynamics (MD) and mesoscopic dynamics (MesoDyn) simulations. Polypropylene (PP) and cellulose are two of most common polymers in textile fibers. Confined amorphous surface layers of PP and cellulose were built successfully with xenon crystals which were used to compact the polymers. The physical and surface properties of the PP and cellulose surface layers were investigated by MD simulations, including the density, cohesive energy, volumetric thermal expansion, and contact angle with water. The topology method was employed to predict the properties of poly(alkylene glycol) (PAG) diblock copolymers and Pluronic triblock copolymers used as lubricants on surfaces. Density, zero shear viscosity, shear module, cohesive energy and solubility parameter were predicted with each block copolymer. Molecular dynamics simulations were used to study the interaction energy per unit contact area of block copolymer melts with PP and cellulose surfaces. The interaction energy is defined as the ratio of interfacial interaction energy to the contact area. Both poly(proplene oxide) (PPO) and poly(ethylene oxide) (PEO) segments provided a lipophilic character to both PP and cellulose surfaces. The PPO/PEO ratio and the molecular weight were found to impact the interaction energy on both PP and cellulose surfaces. In aqueous solutions, the interaction energy is complicated due to the presence of water and the cross interactions between the multiple molecular components. The polymer-water-surface (PWS) calculation method was proposed to calculate such complex systems. In a contrast with a vacuum condition, the presence of water increases the attractive interaction energy of the diblock copolymer on the cellulose surface, compared with that on the PP surface. Water decreases the interaction energy of the triblock copolymer on the cellulose surface, compared with that on the PP surface. MesoDyn was adopted to investigate the self-assembled morphology of the triblock copolymer, in aqueous solution, confined and sheared at solid-liquid interfaces. In a bulk aqueous solution, when the polymer concentration reached 10% v/v, micelles were observed with PPO blocks in the core and PEO blocks in the shell of the micelles. At the concentrations of 25% and 50%, worm-like micelles and irregular cylinders were observed in solutions, respectively. The micelles were formed faster in aqueous solutions confined by cellulose surfaces than that in the bulk. The formed micelles were broken under shearing, which led to a depletion of polymers at the interfaces. During the shearing on the PP surfaces, the polymers were adsorbed on the surfaces protecting the PP surfaces. This simulation study in the fiber lubrication was in good agreement with the experimental results and so provided an approach to visualize the polymer configuration at the liquid-solid interface, predict the lubricant-surface systems, and theoretically guide the experiments of designing new/efficient lubricants for fibers.

Interfacial Properties of Thin Films of Poly(vinyl ether)s with Architectural Design in Water

NASA Astrophysics Data System (ADS)

Oda, Yukari; Itagaki, Nozomi; Sugimoto, Sin; Kawaguchi, Daisuke; Matsuno, Hisao; Tanaka, Keiji

Precise design of primary structure and architecture of polymers leads to the well-defined structure, unique physical properties, and excellent functions not only in the bulk but also at the interfaces. We here constructed functional polymer interfaces in water based on the architectural design of poly(vinyl ether)s with oxyethylene side-chains (POEVE). A branched polymer with POEVE parts was preferentially segregated at the air interface in the matrix of poly(methyl methacrylate). As an alternative way to prepare the POEVE surface, the cross-linked hydrogel thin films were prepared. The moduli of the hydrogel films near the water interfaces, which were examined by force-distance curve measurements using atomic force microscopy, were greatly sensitive to the cross-linking density of the polymers. Diffuse interfaces of POEVE chains at the water interface make it possible to prevent the platelet adhesion on the films.

Release of DNA from polyelectrolyte multilayers fabricated using 'charge-shifting' cationic polymers: tunable temporal control and sequential, multi-agent release.

PubMed

Sun, Bin; Lynn, David M

2010-11-20

We report an approach to the design of multilayered polyelectrolyte thin films (or 'polyelectrolyte multilayers', PEMs) that can be used to provide tunable control over the release of plasmid DNA (or multiple different DNA constructs) from film-coated surfaces. Our approach is based upon methods for the layer-by-layer assembly of DNA-containing thin films, and exploits the properties of a new class of cationic 'charge-shifting' polymers (amine functionalized polymers that undergo gradual changes in net charge upon side chain ester hydrolysis) to provide control over the rates at which these films erode and release DNA. We synthesized two 'charge-shifting' polymers (polymers 1 and 2) containing different side chain structures by ring-opening reactions of poly(2-alkenyl azlactone)s with two different tertiary amine functionalized alcohols (3-dimethylamino-1-propanol and 2-dimethylaminoethanol, respectively). Subsequent characterization revealed large changes in the rates of side chain ester hydrolysis for these two polymers; whereas the half-life for the hydrolysis of the esters in polymer 1 was ~200 days, the half-life for polymer 2 was ~6 days. We demonstrate that these large differences in side chain hydrolysis make possible the design of PEMs that erode and promote the surface-mediated release of DNA either rapidly (e.g., over ~3 days for films fabricated using polymer 2) or slowly (e.g., over ~1 month for films fabricated using polymer 1). We demonstrate further that it is possible to design films with release profiles that are intermediate to these two extremes by fabricating films using solutions containing different mixtures of these two polymers. This approach can thus expand the usefulness of these two polymers and achieve a broader range of DNA release profiles without the need to synthesize polymers with new structures or properties. Finally, we demonstrate that polymers 1 and 2 can be used to fabricate multilayered films with hierarchical structures that promote the sequential release of two different DNA constructs with separate and distinct release profiles (e.g., the release of a first construct over a period of ~3 days, followed by the sustained release of a second for a period of ~70 days). With further development, this approach could contribute to the design of functional thin films and surface coatings that provide sophisticated control over the timing and the order of the release of two or more DNA constructs (or other agents) of interest in a range of biomedical contexts. Copyright © 2010 Elsevier B.V. All rights reserved.

Fibronectin and bovine serum albumin adsorption and conformational dynamics on inherently conducting polymers: a QCM-D study.

PubMed

Molino, Paul J; Higgins, Michael J; Innis, Peter C; Kapsa, Robert M I; Wallace, Gordon G

2012-06-05

Quartz crystal microbalance with dissipation monitoring (QCM-D) was employed to characterize the adsorption of the model proteins, bovine serum albumin (BSA) and fibronectin (FN), to polypyrrole doped with dextran sulfate (PPy-DS) as a function of DS loading and surface roughness. BSA adsorption was greater on surfaces of increased roughness and was above what could be explained by the increase in surface area alone. Furthermore, the additional mass adsorbed on the rough films was concomitant with an increase in the rigidity of the protein layer. Analysis of the dynamic viscoelastic properties of the protein adlayer reveal BSA adsorption on the rough films occurs in two phases: (1) arrival and initial adsorption of protein to the polymer surface and (2) postadsorption molecular rearrangement to a more dehydrated and compact conformation that facilitates further recruitment of protein to the polymer interface, likely forming a multilayer. In contrast, FN adsorption was independent of surface roughness. However, films prepared from solutions containing the highest concentration of DS (20 mg/mL) demonstrated both an increase in adsorbed mass and adlayer viscoelasticity. This is attributed to the higher DS loading in the conducting polymer film resulting in presentation of a more hydrated molecular structure indicative of a more unfolded and bioactive conformation. Modulating the redox state of the PPy-DS polymers was shown to modify both the adsorbed mass and viscoelastic nature of FN adlayers. An oxidizing potential increased both the total adsorbed mass and the adlayer viscoelasticity. Our findings demonstrate that modification of polymer physicochemical and redox condition alters the nature of protein-polymer interaction, a process that may be exploited to tailor the bioactivity of protein through which interactions with cells and tissues may be controlled.

Interfacial welding of dynamic covalent network polymers

NASA Astrophysics Data System (ADS)

Yu, Kai; Shi, Qian; Li, Hao; Jabour, John; Yang, Hua; Dunn, Martin L.; Wang, Tiejun; Qi, H. Jerry

2016-09-01

Dynamic covalent network (or covalent adaptable network) polymers can rearrange their macromolecular chain network by bond exchange reactions (BERs) where an active unit replaces a unit in an existing bond to form a new bond. Such macromolecular events, when they occur in large amounts, can attribute to unusual properties that are not seen in conventional covalent network polymers, such as shape reforming and surface welding; the latter further enables the important attributes of material malleability and powder-based reprocessing. In this paper, a multiscale modeling framework is developed to study the surface welding of thermally induced dynamic covalent network polymers. At the macromolecular network level, a lattice model is developed to describe the chain density evolution across the interface and its connection to bulk stress relaxation due to BERs. The chain density evolution rule is then fed into a continuum level interfacial model that takes into account surface roughness and applied pressure to predict the effective elastic modulus and interfacial fracture energy of welded polymers. The model yields particularly accessible results where the moduli and interfacial strength of the welded samples as a function of temperature and pressure can be predicted with four parameters, three of which can be measured directly. The model identifies the dependency of surface welding efficiency on the applied thermal and mechanical fields: the pressure will affect the real contact area under the consideration of surface roughness of dynamic covalent network polymers; the chain density increment on the real contact area of interface is only dependent on the welding time and temperature. The modeling approach shows good agreement with experiments and can be extended to other types of dynamic covalent network polymers using different stimuli for BERs, such as light and moisture etc.

Retention of 14C-labeled multiwall carbon nanotubes by humic acid and polymers: Roles of macromolecule properties

PubMed Central

Zhao, Qing; Petersen, Elijah J.; Cornelis, Geert; Wang, Xilong; Guo, Xiaoying; Tao, Shu; Xing, Baoshan

2016-01-01

Developing methods to measure interactions of carbon nanotubes (CNTs) with soils and sediments and understanding the impact of soil and sediment properties on CNT deposition are essential for assessing CNT environmental risks. In this study, we utilized functionalized carbon-14 labeled nanotubes to systematically investigate retention of multiwall CNTs (MWCNTs) by 3 humic acids, 3 natural biopolymers, and 10 model solid-phase polymers, collectively termed macromolecules. Surface properties, rather than bulk properties of macromolecules, greatly influenced MWCNT retention. As shown via multiple linear regression analysis and path analysis, aromaticity and surface polarity were the two most positive factors for retention, suggesting retention was regulated by π-π stacking and hydrogen bonding interactions. Moreover, MWCNT deposition was irreversible. These observations may explain the high retention of MWCNT in natural soils. Moreover, our findings on the relative contribution of each macromolecule property on CNT retention provide information on macromolecule selection for removal of MWCNTs from wastewater and provide a method for measuring CNT interactions with organic macromolecules. PMID:27458320

Biomimetic oligosaccharide and peptide surfactant polymers designed for cardiovascular biomaterials

NASA Astrophysics Data System (ADS)

Ruegsegger, Mark Andrew

A common problem associated with cardiovascular devices is surface induced thrombosis initiated by the rapid, non-specific adsorption of plasma proteins onto the biomaterial surface. Control of the initial protein adsorption is crucial to achieve the desired longevity of the implanted biomaterial. The cell membrane glycocalyx acts as a non-thrombogenic interface through passive (dense oligosaccharide structures) and active (ligand/receptor interactions) mechanisms. This thesis is designed to investigate biomimicry of the cell glycocalyx to minimize non-specific protein adsorption and promote specific ligand/receptor interactions. Biomimetic macromolecules were designed through the molecular-scale engineering of polymer surfactants, utilizing a poly(vinyl amine) (PVAm) backbone to which hydrophilic (dextran, maltose, peptide) and hydrophobic alkyl (hexanoyl or hexanal) chains are simultaneously attached. The structure was controlled through the molar feed ratio of hydrophobic-to-hydrophilic groups, which also provided control of the solution and surface-active properties. To mimic passive properties, a series of oligomaltose surfactants were synthesized with increasing saccharide length (n = 2, 7, 15 where n is number of glucose units) to investigate the effect of coating height on protein adsorption. The surfactants were characterized by infra red (IR) and nuclear magnetic resonance (NMR) spectroscopies for structural properties and atomic force microscopy (AFM) and contact angle goniometry for surface activity. Protein adsorption under dynamic flow (5 dyn/cm2) was reduced by 85%--95% over the bare hydrophobic substrate; platelet adhesion dropped by ˜80% compared to glass. Peptide ligands were incorporated into the oligosaccharide surfactant to promote functional activity of the passive coating. The surfactants were synthesized to contain 0%, 25%, 50%, 75%, and 100% peptide ligand density and were stable on hydrophobic surfaces. The peptide surface density was calculated to be 0.86 ligands/nm2 for PVAm(Pep)(100%), as determined by total internal reflection fluorescence (TIRF) spectroscopy. Similar cell growth was observed on the 100% peptide surfactant as for the fibronectin control, and no cell growth was seen on the 0% peptide. Increasing cell viability was observed for the surfaces with increasing peptide density. These results indicate much promise for surfactant polymers in surface modification and the capability to mimic the passive and active properties of the cell glycocalyx.

Tadpole-like artificial micromotor

NASA Astrophysics Data System (ADS)

Liu, Limei; Liu, Mei; Su, Yajun; Dong, Yonggang; Zhou, Wei; Zhang, Lina; Zhang, Hui; Dong, Bin; Chi, Lifeng

2015-01-01

We describe a polymer-based artificial tadpole-like micromotor, which is fabricated through the electrospinning technique. By incorporating functional materials onto its surface or within its body, the resulting tadpole-like micromotor can not only move autonomously in an aqueous solution with a flexible tail, but also exhibit thermo- and magnetic responsive properties.We describe a polymer-based artificial tadpole-like micromotor, which is fabricated through the electrospinning technique. By incorporating functional materials onto its surface or within its body, the resulting tadpole-like micromotor can not only move autonomously in an aqueous solution with a flexible tail, but also exhibit thermo- and magnetic responsive properties. Electronic supplementary information (ESI) available: Experimental section, Fig. S1-S3 and Video S1-S4. See DOI: 10.1039/c4nr06621a

Enhancement of the mechanical properties by graphite flake addition

DOEpatents

Bunnell, Sr., Lee R.

1991-01-01

Compositions in accordance with the invention comprise a polymer and flake reinforcing material distributed throughout the polymer in an effective amount to structurally reinforce the polymer. Individual flakes of the flake material (a) are less than or equal to 1,000 Angstroms in thickness, (b) have an aspect ratio greater than or equal to 100, and (c) are preferably significantly randomly oriented throughout the polymer. A novel apparatus for shear grinding a platy solid material into such individual flakes comprises a cylindrical shearing drum and a shear grinder received therein. The shearing drum has a longitudinal axis and an internal surface formed about a first predetermined radius of curvature. The cylindrical drum is supported for rotation about its longitudinal axis. The shear grinder has an external surface formed about a second predetermined radius of curvature. The second radius of curvature is slightly less than the first radius of curvature.

Well-ordered polymer nano-fibers with self-cleaning property by disturbing crystallization process.

PubMed

Yang, Qin; Luo, Zhuangzhu; Tan, Sheng; Luo, Yimin; Wang, Yunjiao; Zhang, Zhaozhu; Liu, Weimin

2014-01-01

Bionic self-cleaning surfaces with well-ordered polymer nano-fibers are firstly fabricated by disturbing crystallization during one-step coating-curing process. Orderly thin (100 nm) and long (5-10 μm) polymer nano-fibers with a certain direction are fabricated by external macroscopic force (F blow) interference introduced by H2 gas flow, leading to superior superhydrophobicity with a water contact angle (WCA) of 170° and a water sliding angle (WSA) of 0-1°. In contrast, nano-wires and nano-bridges (1-8 μm in length/10-80 nm in width) are generated by "spinning/stretching" under internal microscopic force (F T) interference due to significant temperature difference in the non-uniform cooling medium. The findings provide a novel theoretical basis for controllable polymer "bionic lotus" surface and will further promote practical application in many engineering fields such as drag-reduction and anti-icing.

Well-ordered polymer nano-fibers with self-cleaning property by disturbing crystallization process

NASA Astrophysics Data System (ADS)

Yang, Qin; Luo, Zhuangzhu; Tan, Sheng; Luo, Yimin; Wang, Yunjiao; Zhang, Zhaozhu; Liu, Weimin

2014-07-01

Bionic self-cleaning surfaces with well-ordered polymer nano-fibers are firstly fabricated by disturbing crystallization during one-step coating-curing process. Orderly thin (100 nm) and long (5-10 μm) polymer nano-fibers with a certain direction are fabricated by external macroscopic force ( F blow) interference introduced by H2 gas flow, leading to superior superhydrophobicity with a water contact angle (WCA) of 170° and a water sliding angle (WSA) of 0-1°. In contrast, nano-wires and nano-bridges (1-8 μm in length/10-80 nm in width) are generated by "spinning/stretching" under internal microscopic force ( F T) interference due to significant temperature difference in the non-uniform cooling medium. The findings provide a novel theoretical basis for controllable polymer "bionic lotus" surface and will further promote practical application in many engineering fields such as drag-reduction and anti-icing.

Mechanical comparison of a polymer nanocomposite to a ceramic thin-film anti-reflective filter.

PubMed

Druffel, Thad; Geng, Kebin; Grulke, Eric

2006-07-28

Thin-film filters on optical components have been in use for decades and, for those industries utilizing a polymer substrate, the mismatch in mechanical behaviour has caused problems. Surface damage including scratches and cracks induces haze on the optical filter, reducing the transmission of the optical article. An in-mold anti-reflective (AR) filter incorporating 1/4-wavelength thin films based on a polymer nanocomposite is outlined here and compared with a traditional vacuum deposition AR coating. Nanoindentation and nanoscratch techniques are used to evaluate the mechanical properties of the thin films. Scanning electron microscopy (SEM) images of the resulting indentations and scratches are then compared to the force deflection curves to further explain the phenomena. The traditional coatings fractured by brittle mechanisms during testing, increasing the area of failure, whereas the polymer nanocomposite gave ductile failure with less surface damage.

Magnetic and Dielectric Property Studies in Fe- and NiFe-Based Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Sharma, Himani; Jain, Shubham; Raj, Pulugurtha Markondeya; Murali, K. P.; Tummala, Rao

2015-10-01

Metal-polymer composites were investigated for their microwave properties in the frequency range of 30-1000 MHz to assess their application as inductor cores and electromagnetic isolation shield structures. NiFe and Fe nanoparticles were dispersed in epoxy as nanocomposites, in different volume fractions. The permittivity, permeability, and loss tangents of the composites were measured with an impedance analyzer and correlated with the magnetic properties of the particle such as saturation magnetization and field anisotropy. Fe-epoxy showed lower magnetic permeability but improved frequency stability, compared to the NiFe-epoxy composites of the same volume loading. This is attributed to the differences in nanoparticle's structure such as effective metal core size and particle-porosity distribution in the polymer matrix. The dielectric properties of the nanocomposites were also characterized from 30 MHz to 1000 MHz. The instabilities in the dielectric constant and loss tangent were related to the interfacial polarization relaxation of the particles and the dielectric relaxation of the surface oxides.

Impact of Interfacial Roughness on the Sorption Properties of Nanocast Polymers

DOE PAGES

Sridhar, Manasa; Gunugunuri, Krishna R.; Hu, Naiping; ...

2016-03-16

Nanocasting is an emerging method to prepare organic polymers with regular, nanometer pores using inorganic templates. This report assesses the impact of imperfect template replication on the sorption properties of such polymer castings. Existing X-ray diffraction data show that substantial diffuse scattering exists in the small-angle region even though TEM images show near perfect lattices of uniform pores. To assess the origin of the diffuse scattering, the morphology of the phenol - formaldehyde foams (PFF) was investigated by small-angle X-ray scattering (SAXS). The observed diffuse scattering is attributed to interfacial roughness due to fractal structures. Such roughness has a profoundmore » impact on the sorption properties. Conventional pore- filling models, for example, overestimate protein sorption capacity. A mathematical framework is presented to calculate sorption properties based on observed morphological parameters. The formalism uses the surface fractal dimension determined by SAXS in conjunction with nitrogen adsorption isotherms to predict lysozyme sorption. The results are consistent with measured lysozyme loading.« less

Bactericidal effects of plasma-modified surface chemistry of silicon nanograss

NASA Astrophysics Data System (ADS)

Ostrikov, Kola; Macgregor-Ramiasa, Melanie; Cavallaro, Alex; (Ken Ostrikov, Kostya; Vasilev, Krasimir

2016-08-01

The surface chemistry and topography of biomaterials regulate the adhesion and growth of microorganisms in ways that are still poorly understood. Silicon nanograss structures prepared via inductively coupled plasma etching were coated with plasma deposited nanometer-thin polymeric films to produce substrates with controlled topography and defined surface chemistry. The influence of surface properties on Staphylococcus aureus proliferation is demonstrated and explained in terms of nanograss substrate wetting behaviour. With the combination of the nanograss topography; hydrophilic plasma polymer coatings enhanced antimicrobial activity while hydrophobic coatings reduced it. This study advances the understanding of the effects of surface wettability on the bactericidal properties of reactive nano-engineered surfaces.

Synergistic Interactions of a Synthetic Lubricin-Mimetic with Fibronectin for Enhanced Wear Protection

PubMed Central

Andresen Eguiluz, Roberto C.; Cook, Sierra G.; Tan, Mingchee; Brown, Cory N.; Pacifici, Noah J.; Samak, Mihir S.; Bonassar, Lawrence J.; Putnam, David; Gourdon, Delphine

2017-01-01

Lubricin (LUB), a major mucinous glycoprotein of mammalian synovial fluids, is believed to provide excellent lubrication to cartilage surfaces. Consequently, when joint disease or replacement leads to increased friction and surface damage in the joint, robust synthetic LUB alternatives that could be used therapeutically to improve lubrication and surface protection are needed. Here, we report the characterization of a lubricating multiblock bottlebrush polymer whose architecture was inspired by LUB, and we investigate the role of fibronectin (FN), a glycoprotein found in the superficial zone of cartilage, in mediating the tribological properties of the polymer upon shear between mica surfaces. Our surface forces apparatus (SFA) normal force measurements indicate that the lubricin-mimetic (mimLUB) could be kept anchored between mica surfaces, even under high contact pressures, when an intermediate layer of FN was present. Additional SFA friction measurements show that FN would also extend the wearless friction regime of the polymer up to pressures of 3.4 MPa while ensuring stable friction coefficients (μ ≈ 0.28). These results demonstrate synergistic interactions between mimLUB and FN in assisting the lubrication and wear protection of ideal (mica) substrates upon shear. Collectively, these findings suggest that our proposed mimLUB might be a promising alternative to LUB, as similar mechanisms could potentially facilitate the interaction between the polymer and cartilage surfaces in articular joints and prosthetic implants in vivo. PMID:28702455

3D Printing Polymers with Supramolecular Functionality for Biological Applications.

PubMed

Pekkanen, Allison M; Mondschein, Ryan J; Williams, Christopher B; Long, Timothy E

2017-09-11

Supramolecular chemistry continues to experience widespread growth, as fine-tuned chemical structures lead to well-defined bulk materials. Previous literature described the roles of hydrogen bonding, ionic aggregation, guest/host interactions, and π-π stacking to tune mechanical, viscoelastic, and processing performance. The versatility of reversible interactions enables the more facile manufacturing of molded parts with tailored hierarchical structures such as tissue engineered scaffolds for biological applications. Recently, supramolecular polymers and additive manufacturing processes merged to provide parts with control of the molecular, macromolecular, and feature length scales. Additive manufacturing, or 3D printing, generates customizable constructs desirable for many applications, and the introduction of supramolecular interactions will potentially increase production speed, offer a tunable surface structure for controlling cell/scaffold interactions, and impart desired mechanical properties through reinforcing interlayer adhesion and introducing gradients or self-assembled structures. This review details the synthesis and characterization of supramolecular polymers suitable for additive manufacture and biomedical applications as well as the use of supramolecular polymers in additive manufacturing for drug delivery and complex tissue scaffold formation. The effect of supramolecular assembly and its dynamic behavior offers potential for controlling the anisotropy of the printed objects with exquisite geometrical control. The potential for supramolecular polymers to generate well-defined parts, hierarchical structures, and scaffolds with gradient properties/tuned surfaces provides an avenue for developing next-generation biomedical devices and tissue scaffolds.

Mechanical Properties versus Morphology of Ordered Polymers

DTIC Science & Technology

1980-05-01

for a similar banding observed in PPTA 30 fibers. The dark field results suggest each microfibril ribbon consists of a succession of narrow...transmission electron microscopy may be obtained by surface tension aided microfibril dispersion. The longitudinal sections of fibers obtained by...the value of c ( 0.08) obtained for native and regenerated cellulose , another class of stiff chain polymers16). (Deriva- tives of cellulose can be spun

Polymer composites and porous materials prepared by thermally induced phase separation and polymer-metal hybrid methods

NASA Astrophysics Data System (ADS)

Yoon, Joonsung

The primary objective of this research is to investigate the morphological and mechanical properties of composite materials and porous materials prepared by thermally induced phase separation. High melting crystallizable diluents were mixed with polymers so that the phase separation would be induced by the solidification of the diluents upon cooling. Theoretical phase diagrams were calculated using Flory-Huggins solution thermodynamics which show good agreement with the experimental results. Porous materials were prepared by the extraction of the crystallized diluents after cooling the mixtures (hexamethylbenzene/polyethylene and pyrene/polyethylene). Anisotropic structures show strong dependence on the identity of the diluents and the composition of the mixtures. Anisotropic crystal growth of the diluents was studied in terms of thermodynamics and kinetics using DSC, optical microscopy and SEM. Microstructures of the porous materials were explained in terms of supercooling and dendritic solidification. Dual functionality of the crystallizable diluents for composite materials was evaluated using isotactic polypropylene (iPP) and compatible diluents that crystallize upon cooling. The selected diluents form homogeneous mixtures with iPP at high temperature and lower the viscosity (improved processability), which undergo phase separation upon cooling to form solid particles that function as a toughening agent at room temperature. Tensile properties and morphology of the composites showed that organic crystalline particles have the similar effect as rigid particles to increase toughness; de-wetting between the particle and iPP matrix occurs at the early stage of deformation, followed by unhindered plastic flow that consumes significant amount of fracture energy. The effect of the diluents, however, strongly depends on the identity of the diluents that interact with the iPP during solidification step, which was demonstrated by comparing tetrabromobisphenol-A and phthalic anhydride. A simple method to prepare composite surfaces that can change the wettability in response to the temperature change was proposed and evaluated. Composite surfaces prepared by nanoporous alumina templates filled with polymers showed surface morphology and wettability that depend on temperature. This effect is attributed to the significant difference in thermal conductivity and the thermal expansion coefficient between the alumina and the polymers. The reversibility in thermal response depends on the properties of the polymers.

AFM-based micro/nanoscale lithography of poly(dimethylsiloxane): stick-slip on a softpolymer

NASA Astrophysics Data System (ADS)

Watson, Jolanta A.; Myhra, Sverre; Brown, Christopher L.; Watson, Gregory S.

2005-02-01

Silicone rubbers have steadily gained importance in industry since their introduction in the 1960"s. Poly(dimethylsiloxane) (PDMS) is a relatively soft and optically clear, two-part elastomer with interesting and, more importantly, useful physical and electrical properties. Some of its common applications include protective coatings (e.g., against moisture, environmental attack, mechanical and thermal shock and vibrations), and encapsulation (e.g., amplifiers, inductive coils, connectors and circuit boards). The polymer has attracted recent interest for applications in soft lithography. The polymer is now routinely used as a patterned micro-stamp for chemical modification of surfaces, in particular Au substrates. Prominent stick-slip effects, surface relaxation and elastic recovery were found to be associated with micro/nano manipulation of the polymer by an AFM-based contact mode methodology. Those effects provide the means to explore in detail the meso-scale tip-to-surface interactions between a tip and a soft surface. The dependence of scan speed, loading force, attack angle and number of scan lines have been investigated.

Poly(methyl vinyl ether-alt-maleic acid)-functionalized porous silicon nanoparticles for enhanced stability and cellular internalization.

PubMed

Shahbazi, Mohammad-Ali; Almeida, Patrick V; Mäkilä, Ermei; Correia, Alexandra; Ferreira, Mónica P A; Kaasalainen, Martti; Salonen, Jarno; Hirvonen, Jouni; Santos, Hélder A

2014-03-01

Currently, developing a stable nanocarrier with high cellular internalization and low toxicity is a key bottleneck in nanomedicine. Here, we have developed a successful method to covalently conjugate poly(methyl vinyl ether-co-maleic acid) (PMVE-MA) copolymer on the surface of (3-aminopropyl)triethoxysilane-functionalized thermally carbonized porous silicon nanoparticles (APSTCPSi NPs), forming a surface negatively charged nanovehicle with unique properties. This polymer conjugated NPs could modify surface smoothness, charge, and hydrophilicity of the developed NPs, leading to considerable improvement in the colloidal and plasma stabilities via enhanced suspensibility and charge repulsion. Furthermore, despite the surface negative charge of the polymer-conjugated NPs, the cellular internalization was increased in both MDA-MB-231 and MCF-7 breast cancer cells. These results provide a proof-of-concept evidence that such polymer-based PSi nanocomposite can be extensively used as a promising candidate for intracellular drug delivery. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical monitoring of thin film electro-polymerization on surface of ITO-coated lossy-mode resonance sensor

NASA Astrophysics Data System (ADS)

Sobaszek, Michał; Dominik, Magdalena; Burnat, Dariusz; Bogdanowicz, Robert; Stranak, Viteszlav; Sezemsky, Petr; Śmietana, Mateusz

2017-04-01

This work presents an optical fiber sensors based on lossy-mode resonance (LMR) phenomenon supported by indium tin oxide (ITO) thin overlay for investigation of electro-polymerization effect on ITO's surface. The ITO overlays were deposited on core of polymer-clad silica (PCS) fibers using reactive magnetron sputtering (RMS) method. Since ITO is electrically conductive and electrochemically active it can be used as a working electrode in 3-electrode cyclic voltammetry setup. For fixed potential applied to the electrode current flow decrease with time what corresponds to polymer layer formation on the ITO surface. Since LMR phenomenon depends on optical properties in proximity of the ITO surface, polymer layer formation can be monitored optically in real time. The electrodeposition process has been performed with Isatin which is a strong endogenous neurochemical regulator in humans as it is a metabolic derivative of adrenaline. It was found that optical detection of Isatin is possible in the proposed configuration.

Polymeric surfaces exhibiting photocatalytic activity and controlled anisotropic wettability

NASA Astrophysics Data System (ADS)

Anastasiadis, Spiros H.; Frysali, Melani A.; Papoutsakis, Lampros; Kenanakis, George; Stratakis, Emmanuel; Vamvakaki, Maria; Mountrichas, Grigoris; Pispas, Stergios

2015-03-01

In this work we focus on surfaces, which exhibit controlled, switchable wettability in response to one or more external stimuli as well as photocatalytic activity. For this we are inspired from nature to produce surfaces with a dual-scale hierarchical roughness and combine them with the appropriate inorganic and/or polymer coating. The combination of the hierarchical surface with a ZnO coating and a pH- or temperature-responsive polymer results in efficient photo-active properties as well as reversible superhydrophobic / superhydrophilic surfaces. Furthermore, we fabricate surfaces with unidirectional wettability variation. Overall, such complex surfaces require advanced design, combining hierarchically structured surfaces with suitable polymeric materials. Acknowledgment: This research was partially supported by the European Union (European Social Fund, ESF) and Greek national funds through the ``ARISTEIA II'' Action (SMART-SURF) of the Operational Programme ``Education and Lifelong Learning,'' NSRF 2007-2013, via the General Secretariat for Research & Technology, Ministry of Education and Religious Affairs, Greece.

Tailored Surfaces/Assemblies for Molecular Plasmonics and Plasmonic Molecular Electronics.

PubMed

Lacroix, Jean-Christophe; Martin, Pascal; Lacaze, Pierre-Camille

2017-06-12

Molecular plasmonics uses and explores molecule-plasmon interactions on metal nanostructures for spectroscopic, nanophotonic, and nanoelectronic devices. This review focuses on tailored surfaces/assemblies for molecular plasmonics and describes active molecular plasmonic devices in which functional molecules and polymers change their structural, electrical, and/or optical properties in response to external stimuli and that can dynamically tune the plasmonic properties. We also explore an emerging research field combining molecular plasmonics and molecular electronics.

Protein-Polymer Conjugates: Synthetic Approaches by Controlled Radical Polymerizations & Interesting Applications

PubMed Central

Grover, Gregory N.; Maynard, Heather D.

2011-01-01

Protein-polymer conjugates are of interest to researchers in diverse fields. Attachment of polymers to proteins results in improved pharmacokinetics, which is important in medicine. From an engineering standpoint, conjugates are exciting because they exhibit properties of both the biomolecules and synthetic polymers. This allows the activity of the protein to be altered or tuned, a key aspect in therapeutic design, anchoring conjugates to surfaces, and utilizing these materials for supramolecular self-assembly. Thus, there is broad interest in straightforward synthetic methods to make protein-polymer conjugates. Controlled radical polymerization (CRP) techniques have emerged as excellent strategies to make conjugates because the resulting polymers have narrow molecular weight distributions, targeted molecular weights, and attach to specific sites on proteins. Herein, recent advances in the synthesis and application of protein-polymer conjugates by CRP are highlighted. PMID:21071260

Comparison of Plasma Polymerization under Collisional and Collision-Less Pressure Regimes.

PubMed

Saboohi, Solmaz; Jasieniak, Marek; Coad, Bryan R; Griesser, Hans J; Short, Robert D; Michelmore, Andrew

2015-12-10

While plasma polymerization is used extensively to fabricate functionalized surfaces, the processes leading to plasma polymer growth are not yet completely understood. Thus, reproducing processes in different reactors has remained problematic, which hinders industrial uptake and research progress. Here we examine the crucial role pressure plays in the physical and chemical processes in the plasma phase, in interactions at surfaces in contact with the plasma phase, and how this affects the chemistry of the resulting plasma polymer films using ethanol as the gas precursor. Visual inspection of the plasma reveals a change from intense homogeneous plasma at low pressure to lower intensity bulk plasma at high pressure, but with increased intensity near the walls of the chamber. It is demonstrated that this occurs at the transition from a collision-less to a collisional plasma sheath, which in turn increases ion and energy flux to surfaces at constant RF power. Surface analysis of the resulting plasma polymer films show that increasing the pressure results in increased incorporation of oxygen and lower cross-linking, parameters which are critical to film performance. These results and insights help to explain the considerable differences in plasma polymer properties observed by different research groups using nominally similar processes.

Fabrication of high aspect ratio nanopillars and micro/nano combined structures with hydrophobic surface characteristics by injection molding

NASA Astrophysics Data System (ADS)

Zhou, Mingyong; Xiong, Xiang; Jiang, Bingyan; Weng, Can

2018-01-01

Polymer products with micro/nano-structures have excellent mechanical and optical properties, chemical resistance, and other advantages. Injection molding is one of the most potential techniques to fabricate polymer products with micro/nano-structures artificially in large numbers. In this study, a surface approach to fabricate high aspect ratio nanopillars and micro/nano combined structures was presented. Mold insert with micropillar arrays and nanopillars on its surface was prepared by combing anodic aluminum oxide (AAO) template and etched plate. Anti-sticking modification was done on the template to realize a better demolding quality. The influences of mold temperature and polymer material on the final replication quality were investigated. The results showed that the final replication quality of high aspect ratio nanopillars was greatly improved as compared with the unprocessed template. Polymer with low elongation at break was not suitable to fabricate structures with high aspect ratio via injection molding. For polypropylene surface, the experimental results of static contact angles were almost consistent with Cassie-Baxter equation. When the mold temperature reached 178 °C, hair-like polycarbonate nanopillars were observed, resulting in an excellent hydrophobic characteristic.

Tribochemical synthesis of nano-lubricant films from adsorbed molecules at sliding solid interface: Tribo-polymers from α-pinene, pinane, and n-decane

NASA Astrophysics Data System (ADS)

He, Xin; Barthel, Anthony J.; Kim, Seong H.

2016-06-01

The mechanochemical reactions of adsorbed molecules at sliding interfaces were studied for α-pinene (C10H16), pinane (C10H18), and n-decane (C10H22) on a stainless steel substrate surface. During vapor phase lubrication, molecules adsorbed at the sliding interface could be activated by mechanical shear. Under the equilibrium adsorption condition of these molecules, the friction coefficient of sliding steel surfaces was about 0.2 and a polymeric film was tribochemically produced. The synthesis yield of α-pinene tribo-polymers was about twice as much as pinane tribo-polymers. In contrast to these strained bicyclic hydrocarbons, n-decane showed much weaker activity for tribo-polymerization at the same mechanical shear condition. These results suggested that the mechanical shear at tribological interfaces could induce the opening of the strained ring structure of α-pinene and pinane, which leads to polymerization of adsorbed molecules at the sliding track. On a stainless steel surface, such polymerization reactions of adsorbed molecules do not occur under typical surface reaction conditions. The mechanical properties and boundary lubrication efficiency of the produced tribo-polymer films are discussed.

Antifouling Thin-Film Composite Membranes by Controlled Architecture of Zwitterionic Polymer Brush Layer.

PubMed

Liu, Caihong; Lee, Jongho; Ma, Jun; Elimelech, Menachem

2017-02-21

In this study, we demonstrate a highly antifouling thin-film composite (TFC) membrane by grafting a zwitterionic polymer brush via atom-transfer radical-polymerization (ATRP), a controlled, environmentally benign chemical process. Initiator molecules for polymerization were immobilized on the membrane surface by bioinspired catechol chemistry, leading to the grafting of a dense zwitterionic polymer brush layer. Surface characterization revealed that the modified membrane exhibits reduced surface roughness, enhanced hydrophilicity, and lower surface charge. Chemical force microscopy demonstrated that the modified membrane displayed foulant-membrane interaction forces that were 1 order of magnitude smaller than those of the pristine TFC membrane. The excellent fouling resistance imparted by the zwitterionic brush layer was further demonstrated by significantly reduced adsorption of proteins and bacteria. In addition, forward osmosis fouling experiments with a feed solution containing a mixture of organic foulants (bovine-serum albumin, alginate, and natural organic matter) indicated that the modified membrane exhibited significantly lower water flux decline compared to the pristine TFC membrane. The controlled architecture of the zwitterionic polymer brush via ATRP has the potential for a facile antifouling modification of a wide range of water treatment membranes without compromising intrinsic transport properties.

Surface modification of carbon nanotubes using 3-aminopropyltriethoxysilane to improve mechanical properties of nanocomposite based polymer matrix: Experimental and Density functional theory study

NASA Astrophysics Data System (ADS)

Hamed Mashhadzadeh, A.; Fereidoon, Ab.; Ghorbanzadeh Ahangari, M.

2017-10-01

In current study we combined theoretical and experimental studies to evaluate the effect of functionalization and silanization on mechanical behavior of polymer-based/CNT nanocomposites. Epoxy was selected as thermoset polymer, polypropylene and poly vinyl chloride were selected as thermoplastic polymers. The whole procedure is divided to two sections . At first we applied density functional theory (DFT) to analyze the effect of functionalization on equilibrium distance and adsorption energy of unmodified, functionalized by sbnd OH group and silanized epoxy/CNT, PP/CNT and PVC/CNT nanocomposites and the results showed that functionalization increased adsorption energy and reduced the equilibrium distance in all studied nanocomposites and silanization had higher effect comparing to OH functionalizing. Then we prepared experimental samples of all mentioned nanocomposites and tested their tensile and flexural strength properties. The obtained results showed that functionalization increased the studied mechanical properties in all evaluated nanocomposites. Finally we compared the results of experimental and theoretical sections with each other and estimated a suitable agreement between these parts.

Thiolated poly(ɛ-caprolactone) macroligand with vacant coordination sites on gold substrate: Synthesis and surface characterization

NASA Astrophysics Data System (ADS)

Farah, Abdiaziz A.; Zheng, Susan H.; Morin, Sylvie; Bensebaa, Farid; Pietro, William J.

2007-04-01

Surface-confined telechelic poly(ɛ-caprolactone) macroligand with two distinct functional groups per polymeric chain has been synthesized and characterized. The molecular microstructure of the macroligand with regard to the properties of the end-capped functionalities and with those on surface substrate has been studied by solution and surface analytical methods (i.e., X-ray photoelectron spectroscopy (XPS), grazing angle reflectance-Fourier transform IR spectroscopy (GA-FTIR), water contact angle measurements, and atomic force microscopy (AFM)) to elucidate the structure and properties of such multifunctional polymer on gold (1 1 1) substrate.

Directed aggregation of carbon nanotube on curved surfaces by polymer induced depletion attraction

NASA Astrophysics Data System (ADS)

Lee, Hsin-Chieh; Jiang, Hong-Ren

2017-12-01

In this study, we show that by chemically grafting macromolecule, polyethylene glycol (PEG), onto CNTs, PEG-CNTs become dispersible in an aqueous solution with tunable depletion interactions with each other. The aggregation of the PEG-CNTs can be controlled by adding PEG polymers into the solution. PEG-CNTs not only aggregate with each other but also tend to aggregate on curved surfaces. Due to this property, we show that PEG-CNTs can be directed to aggregate on particles and patterned surfaces. Depletion interaction induced aggregation of PEG-CNTs may provide a method to place PEG-CNTs on a specific position for different applications ranging from biomedical to industrial usages.

Investigation of test methods, material properties and processes for solar cell encapsulants

NASA Technical Reports Server (NTRS)

Willis, P. B.

1985-01-01

The historical development of ethylene vinyl acetate (EVA) is presented, including the functional requirements, polymer selection, curing, stabilization, production and module processing. The construction and use of a new method for the accelerated aging of polymers is detailed. The method more closely resembles the conditions that may be encountered in actual module field exposure and additionally may permit service life to be predicted accurately. The use of hardboard as a low cost candidate substrate material is studied. The performance of surface antisoiling treatments useful for imparting a self cleaning property to modules is updated.

Stimuli-responsive polymers for antimicrobial therapy: drug targeting, contact-killing surfaces and competitive release.

PubMed

Alvarez-Lorenzo, Carmen; Garcia-Gonzalez, Carlos A; Bucio, Emilio; Concheiro, Angel

2016-08-01

Polymers can be designed to modify their features as a function of the level and nature of the surrounding microorganisms. Such responsive polymers can endow drug delivery systems and drug-medical device combination products with improved performance against intracellular infections and biofilms. Knowledge on microorganism growth environment outside and inside cells and formation of biofilm communities on biological and synthetic surfaces, together with advances in materials science and drug delivery are prompting strategies with improved efficacy and safety compared to traditional systemic administration of antimicrobial agents. This review deals with antimicrobial strategies that rely on: (i) polymers that disintegrate or undergo phase-transitions in response to changes in enzymes, pH and pO2 associated to microorganism growth; (ii) stimuli-responsive polymers that expose contact-killing groups when microorganisms try to adhere; and (iii) bioinspired polymers that recognize microorganisms for triggered (competitive/affinity-driven) drug release. Prophylaxis and treatment of infections may benefit from polymers that are responsive to the unique changes that microbial growth causes in the surrounding environment or that even recognize the microorganism itself or its quorum sensing signals. These polymers may offer novel tools for the design of macrophage-, bacteria- and/or biofilm-targeted nanocarriers as well as of medical devices with switchable antibiofouling properties.

Composite fabrication and polymer modification using neoteric solvents

NASA Astrophysics Data System (ADS)

Eastman, Scott A.

This thesis is divided into two research initiatives: The fabrication and study of bulk, co-continuous, cellulosic-polymer composites with the aid of supercritical CO2 (SC CO2); and the study of poly(vinyl alcohol) (PVOH) modification and surface activity in ionic liquids. The first part of this thesis utilizes the tunable solubility, gas-like diffusivity, and omniphilic wettability of SC CO2 to incorporate and subsequently polymerize silicone and poly(enemer) prepolymer mixtures throughout various cellulosic substrates. Chapters two and three investigate the mechanical properties of these composites and demonstrate that nearly every resulting composite demonstrates an improved flexural modulus and energy release rate upon splitting. Fire resistance of these composites was also investigated and indicates that the heat release rate, total heat released, and char yield were significantly improved upon for all silicone composites compared to the untreated cellulosic material. Chapter four looks specifically at aspen-silicone composites for thermo-oxidative studies under applied loads in order to study the effect of silicone incorporation on the failure kinetics of aspen. The aspen-silicone composites tested under these conditions demonstrated significantly longer lifetimes under the same loading and heating conditions compared with untreated aspen. The second part of this thesis focuses on studying ionic liquids as potentially useful solvents and reaction media for poly(vinyl alcohol). Two ionic liquids (1-Butyl-3-methylimidizolium chloride and tributylethylphosphonium diethylphosphate) were found to readily dissolve PVOH. More importantly, we have demonstrated that these solvents can be used as inert reaction media for PVOH modification. Both ionic liquids were found to facilitate the quantitative esterification of PVOH, while only the phosphonium ionic liquid supports the quantitative urethanation of the polymer. In an attempt to tune the surface properties of ionic liquid/polymer solutions, PVOH was also partially esterified with low surface energy substituents. Both surface tension and surface composition of the ionic liquid/polymer solutions can be manipulated by the stoichiometric addition of low surface energy acid chlorides. This work on the modification of PVOH can be directly applied to the modification of polysaccharides such as cellulose which could have important implications from a sustainability and energy standpoint.

Metal-dielectric interactions

NASA Technical Reports Server (NTRS)

Buckley, D. H.

1979-01-01

Metal direlectric surface interactions and dielectric films on metal substrates were investigated. Since interfacial interaction depends so heavily on the nature of the surfaces, analytical surface tools such as Auger emission spectroscopy, X-ray photoelectron spectroscopy and field ion microscopy were used to assist in surface and interfacial characterization. The results indicate that with metals contacting certain glasses in the clean state interfacial, bonding produces fractures in the glasses while when a film such as water is present, fractures occur in the metal near the interface. Friction forces were used to measure the interfacial bond strengths. Studies with metals contacting polymers using field ion microscopy revealed that strong bonding forces could develop being between a metal and polymer surface with polymer transferring to the metal surface in various ways depending upon the forces applied to the surface in contact. With the deposition of refractory carbides, silicides and borides onto metal and alloy substrates the presence of oxides at the interface or active gases in the deposition plasma were shown to alter interfacial properties and chemistry. Auger ion depth profile analysis indicated the chemical composition at the interface and this could be related to the mechanical, friction, and wear behavior of the coating.

Effect of alkali treatment on the physical and surface properties of Indian hemp fibers

NASA Astrophysics Data System (ADS)

Sangappa, Rao, B. Lakshmeesha; Asha, S.; Somashekar, R.

2013-02-01

The Plant fibers are rich in cellulose and they are a cheap, easily renewable source of fibers with the potential for polymer reinforcement. The presence of surface impurities and the large amount of hydroxyl groups make plant fibers less attractive for reinforcement of polymeric materials. Hemp (Cannabis Sativa L.) fibers were subjected to alkalization using 1N sodium hydroxide (NaOH). The structural properties and surface morphology of untreated and chemically modified fibers have been studied using X-ray diffraction (WAXS) and Scanning electron microscopy (SEM) respectively.

Affects of Microgravity on the Polymerization and Material Properties of Biomedical Grade Polymers

NASA Astrophysics Data System (ADS)

Crane, Deborah J.

2002-01-01

the material of choice in the production of acetabular cups for hip and tibial cradles for knee orthopeadic implant components for over 30 years. Although UHMWPE is used for more than 1.5 million implants a year in the United States alone and more than 3 million implant surgeries a year worldwide, problems with debris particle formation, pitting and fracture continue to induce premature failure of implant components. chains produced during polymerization are capable of packing into crystalline structures called lamellae, which are embedded within randomly oriented amorphous regions. Crosslinks, or tie molecules bridge the crystalline structures, which contribute to the materials' toughness and strength as a biomedical material. Research has been conducted providing evidence that a crosslinked gradient at the articulating surface of the polymer component provides resistance to surface degradation and subsequent debris formation. Recently, the introduction of highly crosslinked UHMWPE had proven to reduce some of the problems associated with the applications of this polymer as a biomedical material and was seen as the answer to solving the continuing problems associated with UHMWPE implant components. Yet current research into the fatigue characteristics of highly crosslinked UHMWPE has shown that subsurface crack propagation and subsequent delamination continues to produce problematic debris generation. Studies have shown that various sterilization and accelerated aging (to emulate natural oxidation rates) protocols adversely effects the material properties. Additional research has shown that alignment of the lamellae, caused by processing technique, fabrication or surface articulation may be the precursor to debris particle formation. Processing techniques performed under high pressure has proven to effect the width of the crystalline lamellae and therefore, the material's response to wear and fracture. UHMWP due to a microgravity environment, which could be extended to include other polymers. Polymerization as well as polymer processing in a microgravity environment may affect the length and orientation of the molecular chains, the degree of crosslinking, and distribution of amorphous to crystalline portions of the material, thus changing the ultimate properties of the polymer. Small polymer samples would be produced from the resin for testing and analysis. This research would include the effect of micro-g processing by compression molded vs. ram extruded samples for analysis. Morphological alterations in the material could be monitored using Transmission Electron Microscopy and associated properties such as toughness, density and crystallinity could be determined and compared to terra produced materials using conventional mechanical testing, density gradient columns and calorimetry techniques. If alterations are evident, fatigue testing can be performed on small specimens in order to determine the material's resistance to crack initiation and propagation. number of orthopaedic implant recipients and could be extended for use in robotics and other beneficial applications. Although polymers exhibit the greatest biocompatibility, problems with debris particle generation continue to reduce the effectiveness of UHMWPE as a biomedical material. Further polymer research in a microgravity environment may prove to produce the desired alterations in the materials' morphology and associated properties, therefore providing millions of people with superior orthopaedic implant components and lessen the occurrences of repeat surgery.

Efficacy of Natural Polymer Derivatives on Soil Physical Properties and Erosion on an Experimental Loess Hillslope.

PubMed

Liu, Jun'e; Wang, Zhanli; Li, Yuanyuan

2017-12-22

Raindrops disperse large soil aggregates into smaller particles, which can clog soil pores, cause soil crusting, reduce rainfall infiltration and increase soil loss. It was found that natural polymer derivatives were effective in improving soil physical properties and decreasing soil erosion on an experimental loess hillslope. This study investigated the effect of new natural polymer derivatives (Jag S and Jag C162) on soil properties, rainfall infiltration and sediment yield at four rates of sprayed polymers (0, 1, 3 and 5 g/m²), three rainfall intensities (1, 1.5 and 2 mm/min) and a slope gradient of 15° with a silt loam soil through simulated rain. The results showed that both Jag S and Jag C162 significantly increased the shear strength and improved the aggregates composition of the soil surface. The water-stable soil aggregates >0.25 mm increased from 9% to 50% with increasing rates of Jag S and Jag C162. Jag S and Jag C162 also effectively increased rainfall infiltration and final infiltration rate, and reduced erosion compared to controls without natural polymer derivatives added. However, higher rates of Jag S produced lower infiltration rates. Although both Jag S and Jag C162 effectively influenced soil physical properties and erosion, the effect of Jag C162 was more significant than that of Jag S.

Efficacy of Natural Polymer Derivatives on Soil Physical Properties and Erosion on an Experimental Loess Hillslope

PubMed Central

Liu, Jun’e; Wang, Zhanli; Li, Yuanyuan

2017-01-01

Raindrops disperse large soil aggregates into smaller particles, which can clog soil pores, cause soil crusting, reduce rainfall infiltration and increase soil loss. It was found that natural polymer derivatives were effective in improving soil physical properties and decreasing soil erosion on an experimental loess hillslope. This study investigated the effect of new natural polymer derivatives (Jag S and Jag C162) on soil properties, rainfall infiltration and sediment yield at four rates of sprayed polymers (0, 1, 3 and 5 g/m2), three rainfall intensities (1, 1.5 and 2 mm/min) and a slope gradient of 15° with a silt loam soil through simulated rain. The results showed that both Jag S and Jag C162 significantly increased the shear strength and improved the aggregates composition of the soil surface. The water-stable soil aggregates >0.25 mm increased from 9% to 50% with increasing rates of Jag S and Jag C162. Jag S and Jag C162 also effectively increased rainfall infiltration and final infiltration rate, and reduced erosion compared to controls without natural polymer derivatives added. However, higher rates of Jag S produced lower infiltration rates. Although both Jag S and Jag C162 effectively influenced soil physical properties and erosion, the effect of Jag C162 was more significant than that of Jag S. PMID:29271899

Coated carbon nanotube array electrodes

DOEpatents

Ren, Zhifeng; Wen, Jian; Chen, Jinghua; Huang, Zhongping; Wang, Dezhi

2006-12-12

The present invention provides conductive carbon nanotube (CNT) electrode materials comprising aligned CNT substrates coated with an electrically conducting polymer, and the fabrication of electrodes for use in high performance electrical energy storage devices. In particular, the present invention provides conductive CNTs electrode material whose electrical properties render them especially suitable for use in high efficiency rechargeable batteries. The present invention also provides methods for obtaining surface modified conductive CNT electrode materials comprising an array of individual linear, aligned CNTs having a uniform surface coating of an electrically conductive polymer such as polypyrrole, and their use in electrical energy storage devices.

Coated carbon nanotube array electrodes

DOEpatents

Ren, Zhifeng [Newton, MA; Wen, Jian [Newton, MA; Chen, Jinghua [Chestnut Hill, MA; Huang, Zhongping [Belmont, MA; Wang, Dezhi [Wellesley, MA

2008-10-28

The present invention provides conductive carbon nanotube (CNT) electrode materials comprising aligned CNT substrates coated with an electrically conducting polymer, and the fabrication of electrodes for use in high performance electrical energy storage devices. In particular, the present invention provides conductive CNTs electrode material whose electrical properties render them especially suitable for use in high efficiency rechargeable batteries. The present invention also provides methods for obtaining surface modified conductive CNT electrode materials comprising an array of individual linear, aligned CNTs having a uniform surface coating of an electrically conductive polymer such as polypyrrole, and their use in electrical energy storage devices.

Crystallization features of normal alkanes in confined geometry.

PubMed

Su, Yunlan; Liu, Guoming; Xie, Baoquan; Fu, Dongsheng; Wang, Dujin

2014-01-21

How polymers crystallize can greatly affect their thermal and mechanical properties, which influence the practical applications of these materials. Polymeric materials, such as block copolymers, graft polymers, and polymer blends, have complex molecular structures. Due to the multiple hierarchical structures and different size domains in polymer systems, confined hard environments for polymer crystallization exist widely in these materials. The confined geometry is closely related to both the phase metastability and lifetime of polymer. This affects the phase miscibility, microphase separation, and crystallization behaviors and determines both the performance of polymer materials and how easily these materials can be processed. Furthermore, the size effect of metastable states needs to be clarified in polymers. However, scientists find it difficult to propose a quantitative formula to describe the transition dynamics of metastable states in these complex systems. Normal alkanes [CnH2n+2, n-alkanes], especially linear saturated hydrocarbons, can provide a well-defined model system for studying the complex crystallization behaviors of polymer materials, surfactants, and lipids. Therefore, a deeper investigation of normal alkane phase behavior in confinement will help scientists to understand the crystalline phase transition and ultimate properties of many polymeric materials, especially polyolefins. In this Account, we provide an in-depth look at the research concerning the confined crystallization behavior of n-alkanes and binary mixtures in microcapsules by our laboratory and others. Since 2006, our group has developed a technique for synthesizing nearly monodispersed n-alkane containing microcapsules with controllable size and surface porous morphology. We applied an in situ polymerization method, using melamine-formaldehyde resin as shell material and nonionic surfactants as emulsifiers. The solid shell of microcapsules can provide a stable three-dimensional (3-D) confining environment. We have studied multiple parameters of these microencapsulated n-alkanes, including surface freezing, metastability of the rotator phase, and the phase separation behaviors of n-alkane mixtures using differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD), and variable-temperature solid-state nuclear magnetic resonance (NMR). Our investigations revealed new direct evidence for the existence of surface freezing in microencapsulated n-alkanes. By examining the differences among chain packing and nucleation kinetics between bulk alkane solid solutions and their microencapsulated counterparts, we also discovered a mechanism responsible for the formation of a new metastable bulk phase. In addition, we found that confinement suppresses lamellar ordering and longitudinal diffusion, which play an important role in stabilizing the binary n-alkane solid solution in microcapsules. Our work also provided new insights into the phase separation of other mixed system, such as waxes, lipids, and polymer blends in confined geometry. These works provide a profound understanding of the relationship between molecular structure and material properties in the context of crystallization and therefore advance our ability to improve applications incorporating polymeric and molecular materials.

Photoswitching of glass transition temperatures of azobenzene-containing polymers induces reversible solid-to-liquid transitions.

PubMed

Zhou, Hongwei; Xue, Changguo; Weis, Philipp; Suzuki, Yasuhito; Huang, Shilin; Koynov, Kaloian; Auernhammer, Günter K; Berger, Rüdiger; Butt, Hans-Jürgen; Wu, Si

2017-02-01

The development of polymers with switchable glass transition temperatures (T g ) can address scientific challenges such as the healing of cracks in high-T g polymers and the processing of hard polymers at room temperature without using plasticizing solvents. Here, we demonstrate that light can switch the T g of azobenzene-containing polymers (azopolymers) and induce reversible solid-to-liquid transitions of the polymers. The azobenzene groups in the polymers exhibit reversible cis-trans photoisomerization abilities. Trans azopolymers are solids with T g above room temperature, whereas cis azopolymers are liquids with T g below room temperature. Because of the photoinduced solid-to-liquid transitions of these polymers, light can reduce the surface roughness of azopolymer films by almost 600%, repeatedly heal cracks in azopolymers, and control the adhesion of azopolymers for transfer printing. The photoswitching of T g provides a new strategy for designing healable polymers with high T g and allows for control over the mechanical properties of polymers with high spatiotemporal resolution.

Redox-responsive self-healing materials formed from host–guest polymers

PubMed Central

Nakahata, Masaki; Takashima, Yoshinori; Yamaguchi, Hiroyasu; Harada, Akira

2011-01-01

Expanding the useful lifespan of materials is becoming highly desirable, and self-healing and self-repairing materials may become valuable commodities. The formation of supramolecular materials through host–guest interactions is a powerful method to create non-conventional materials. Here we report the formation of supramolecular hydrogels and their redox-responsive and self-healing properties due to host–guest interactions. We employ cyclodextrin (CD) as a host molecule because it is environmentally benign and has diverse applications. A transparent supramolecular hydrogel quickly forms upon mixing poly(acrylic acid) (pAA) possessing β-CD as a host polymer with pAA possessing ferrocene as a guest polymer. Redox stimuli induce a sol−gel phase transition in the supramolecular hydrogel and can control self-healing properties such as re-adhesion between cut surfaces. PMID:22027591

Composite materials obtained by the ion-plasma sputtering of metal compound coatings on polymer films

NASA Astrophysics Data System (ADS)

Khlebnikov, Nikolai; Polyakov, Evgenii; Borisov, Sergei; Barashev, Nikolai; Biramov, Emir; Maltceva, Anastasia; Vereshchagin, Artem; Khartov, Stas; Voronin, Anton

2016-01-01

In this article, the principle and examples composite materials obtained by deposition of metal compound coatings on polymer film substrates by the ion-plasma sputtering method are presented. A synergistic effect is to obtain the materials with structural properties of the polymer substrate and the surface properties of the metal deposited coatings. The technology of sputtering of TiN coatings of various thicknesses on polyethylene terephthalate films is discussed. The obtained composites are characterized by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), atomic force microscopy (AFM), and scanning tunneling microscopy (STM) is shown. The examples of application of this method, such as receiving nanocomposite track membranes and flexible transparent electrodes, are considered.

Glass transition behavior of polystyrene/silica nanocomposites.

NASA Astrophysics Data System (ADS)

Xie, Yuping; Sen, Sudeepto; Kumar, Sanat; Bansal, Amitabh

2006-03-01

The change in thermomechanical properties of nano-filled polymers is of considerable scientific and technological interest. The interaction between the nanofillers and the matrix polymer controls the nanocomposite properties. We will present the results from recent and ongoing DSC experiments on polystyrene/silica nanocomposites. Polystyrene of different molecular weights (and from different sources) and silica nanoparticles 10-15 nm in diameter (both as received from Nissan and surface modified by grafted or physisorbed polystyrene) are being used to process the nanocomposites. We are studying trends in the glass transition behavior by changing the matrix molecular weights and the silica weight fractions. Recent data indicate that the glass transition temperature can both decrease and increase depending on the polymer-nanofiller combination as well as the thermal treatment of the nanocomposites prior to the DSC runs.

Natural and synthetic polymers in fabric and home care applications

NASA Astrophysics Data System (ADS)

Paderes, Monissa; Ahirwal, Deepak; Fernández Prieto, Susana

2017-07-01

Polymers can be tailored to provide different benefits in Fabric & Home Care formulations depending on the monomers and modifications used, such as avoiding dye transfer inhibition in the wash, modifying the surface of tiles or increasing the viscosity and providing suspension properties to consumer products. Specifically, the rheology modification properties of synthetic and natural polymers are discussed in this chapter. The choice of a polymeric rheology modifier will depend on the formulation ingredients (charges, functional groups), the type and the amount of surfactants, the pH and the desired rheology modification. Natural polymeric rheology modifiers have been traditionally used in the food industry, being xanthan gum one of the most well-known ones. On the contrary, synthetic rheology modifiers are preferably used in paints & coats, textile printing and cleaning products.

Universal Surface-initiated Polymerization of Antifouling Zwitterionic Brushes Using A Mussel-Mimetic Peptide Initiator

PubMed Central

Kuang, Jinghao; Messersmith, Phillip B.

2012-01-01

We report a universal method for the surface-initated polymerization (SIP) of a antifouling polymer brush on various classes of surfaces, including noble metals, metal oxides and inert polymers. Inspired by the versatility of mussel adhesive proteins, we synthesized a novel bifunctional tripeptide bromide (BrYKY) which combines an atom transfer radical polymerization (ATRP) initiating alkyl bromide with l-3,4-dihydroxyphenylalanine (DOPA) and lysine. Simple dip-coating of substrates with variable wetting properties and compositions, including Teflon®, in a BrYKY solution at pH 8.5 led to formation of a thin film of cross-linked BrYKY. Subsequently, we showed that the BrYKY layer initiated the ATRP of a zwitterionic monomer, sulfobetaine methacrylate (SBMA) on all substrates, resulting in high density antifouling pSBMA brushes. Both BrYKY deposition and pSBMA grafting were unambiguously confirmed by ellipsometry, X-ray photoelectron spectroscopy and goniometry. All substrates that were coated with BrYKY/pSBMA dramatically reduced bacterial adhesion for 24 h and also resisted mammalian cell adhesion for at least 4 months, demonstrating the long-term stability of the BrYKY anchoring and antifouling properties of pSBMA. The use of BrYKY as a primer and polymerization initiator has the potential to be widely employed in surface grafted polymer brush modifications for biomedical and other applications. PMID:22506651

Molecular Approach to Conjugated Polymers with Biomimetic Properties.

PubMed

Baek, Paul; Voorhaar, Lenny; Barker, David; Travas-Sejdic, Jadranka

2018-06-13

The field of bioelectronics involves the fascinating interplay between biology and human-made electronics. Applications such as tissue engineering, biosensing, drug delivery, and wearable electronics require biomimetic materials that can translate the physiological and chemical processes of biological systems, such as organs, tissues. and cells, into electrical signals and vice versa. However, the difference in the physical nature of soft biological elements and rigid electronic materials calls for new conductive or electroactive materials with added biomimetic properties that can bridge the gap. Soft electronics that utilize organic materials, such as conjugated polymers, can bring many important features to bioelectronics. Among the many advantages of conjugated polymers, the ability to modulate the biocompatibility, solubility, functionality, and mechanical properties through side chain engineering can alleviate the issues of mechanical mismatch and provide better interface between the electronics and biological elements. Additionally, conjugated polymers, being both ionically and electrically conductive through reversible doping processes provide means for direct sensing and stimulation of biological processes in cells, tissues, and organs. In this Account, we focus on our recent progress in molecular engineering of conjugated polymers with tunable biomimetic properties, such as biocompatibility, responsiveness, stretchability, self-healing, and adhesion. Our approach is general and versatile, which is based on functionalization of conjugated polymers with long side chains, commonly polymeric or biomolecules. Applications for such materials are wide-ranging, where we have demonstrated conductive, stimuli-responsive antifouling, and cell adhesive biointerfaces that can respond to external stimuli such as temperature, salt concentration, and redox reactions, the processes that in turn modify and reversibly switch the surface properties. Furthermore, utilizing the advantageous chemical, physical, mechanical and functional properties of the grafts, we progressed into grafting of the long side chains onto conjugated polymers in solution, with the vision of synthesizing solution-processable conjugated graft copolymers with biomimetic functionalities. Examples of the developed materials to date include rubbery and adhesive photoluminescent plastics, biomolecule-functionalized electrospun biosensors, thermally and dually responsive photoluminescent conjugated polymers, and tunable self-healing, adhesive, and stretchable strain sensors, advanced functional biocidal polymers, and filtration membranes. As outlined in these examples, the applications of these biomimetic, conjugated polymers are still in the development stage toward truly printable, organic bioelectronic devices. However, in this Account, we advocate that molecular engineering of conjugated polymers is an attractive approach to a versatile class of organic electronics with both ionic and electrical conductivity as well as mechanical properties required for next-generation bioelectronics.

Carbon Redox-Polymer-Gel Hybrid Supercapacitors

PubMed Central

Vlad, A.; Singh, N.; Melinte, S.; Gohy, J.-F.; Ajayan, P.M.

2016-01-01

Energy storage devices that provide high specific power without compromising on specific energy are highly desirable for many electric-powered applications. Here, we demonstrate that polymer organic radical gel materials support fast bulk-redox charge storage, commensurate to surface double layer ion exchange at carbon electrodes. When integrated with a carbon-based electrical double layer capacitor, nearly ideal electrode properties such as high electrical and ionic conductivity, fast bulk redox and surface charge storage as well as excellent cycling stability are attained. Such hybrid carbon redox-polymer-gel electrodes support unprecedented discharge rate of 1,000C with 50% of the nominal capacity delivered in less than 2 seconds. Devices made with such electrodes hold the potential for battery-scale energy storage while attaining supercapacitor-like power performances. PMID:26917470

The immobilization of a direct thrombin inhibitor to a polyurethane as a nonthrombogenic surface coating for extracorporeal circulation.

PubMed

Yu, Jane; Brisbois, Elizabeth; Handa, Hitesh; Annich, Gail; Meyerhoff, Mark; Bartlett, Robert; Major, Terry

2016-04-07

A biomaterial with both antithrombin and antiplatelet properties is the ideal surface for use in extracorporeal circulation (ECC) as it targets both fibrin generation and platelet adhesion. A hemocompatible surface coating avoids the need for systemic anticoagulation by providing a local anticoagulant effect at the polymer-blood interface. Previous work has demonstrated the potential use of argatroban, a direct thrombin inhibitor, as a nonthrombogenic material for extracorporeal devices. The work reported here focuses on the characterization of argatroban linked to a polyurethane-silicone polymer, CarboSil®. Chemical immobilization, the amount of argatroban, incubation times, and saturation point were evaluated to achieve maximal antithrombin activity at the polymer surface. Cross-linked polymer coatings reacted with 10 and 30 µmole of argatroban were prepared and tested. These coatings resulted in argatroban activity levels of 0.131 µM and 0.446 µM, respectively. After refining the cross-linking process, argatroban activity increased by approximately 3.6 fold. Maintenance of activity and leaching from the polymer surface were also evaluated. Using the refined process for linking argatroban to polymer, the resulting polymer was applied as a surface coating to the inner lumen of poly(vinyl chloride) ECC circuit tubing and its antithrombin effect evaluated using a 4 h rabbit ECC model. Following 4 h of blood exposure, the argatroban circuit demonstrated significantly less thrombus formation compared to the control CarboSil® coating with a 4.1 cm 2 thrombus average area for the control coating compared to 1.2 cm 2 for the argatroban coating (n=4). There was no significant change in thrombin time from baseline in plasma from animals in which the argatroban coated circuit was used, with a thrombin time of 16.2 s at t=0 and 14.5 s after 4 h. These results demonstrate the potential efficacy of immobilized argatroban as a hemocompatible biomaterial for extracorporeal life support devices.

The immobilization of a direct thrombin inhibitor to a polyurethane as a nonthrombogenic surface coating for extracorporeal circulation

PubMed Central

Yu, Jane; Brisbois, Elizabeth; Handa, Hitesh; Annich, Gail; Meyerhoff, Mark; Bartlett, Robert; Major, Terry

2016-01-01

A biomaterial with both antithrombin and antiplatelet properties is the ideal surface for use in extracorporeal circulation (ECC) as it targets both fibrin generation and platelet adhesion. A hemocompatible surface coating avoids the need for systemic anticoagulation by providing a local anticoagulant effect at the polymer-blood interface. Previous work has demonstrated the potential use of argatroban, a direct thrombin inhibitor, as a nonthrombogenic material for extracorporeal devices. The work reported here focuses on the characterization of argatroban linked to a polyurethane-silicone polymer, CarboSil®. Chemical immobilization, the amount of argatroban, incubation times, and saturation point were evaluated to achieve maximal antithrombin activity at the polymer surface. Cross-linked polymer coatings reacted with 10 and 30 µmole of argatroban were prepared and tested. These coatings resulted in argatroban activity levels of 0.131 µM and 0.446 µM, respectively. After refining the cross-linking process, argatroban activity increased by approximately 3.6 fold. Maintenance of activity and leaching from the polymer surface were also evaluated. Using the refined process for linking argatroban to polymer, the resulting polymer was applied as a surface coating to the inner lumen of poly(vinyl chloride) ECC circuit tubing and its antithrombin effect evaluated using a 4 h rabbit ECC model. Following 4 h of blood exposure, the argatroban circuit demonstrated significantly less thrombus formation compared to the control CarboSil® coating with a 4.1 cm2 thrombus average area for the control coating compared to 1.2 cm2 for the argatroban coating (n=4). There was no significant change in thrombin time from baseline in plasma from animals in which the argatroban coated circuit was used, with a thrombin time of 16.2 s at t=0 and 14.5 s after 4 h. These results demonstrate the potential efficacy of immobilized argatroban as a hemocompatible biomaterial for extracorporeal life support devices. PMID:27458521

Targeted delivery of 10-hydroxycamptothecin to human breast cancers by cyclic RGD-modified lipid-polymer hybrid nanoparticles.

PubMed

Yang, Zhe; Luo, Xingen; Zhang, Xiaofang; Liu, Jie; Jiang, Qing

2013-04-01

Lipid-polymer hybrid nanoparticles (NPs) combining the positive attributes of both liposomes and polymeric NPs are increasingly being considered as promising candidates to carry therapeutic agents safely and efficiently into targeted sites. Herein, a modified emulsification technique was developed and optimized for the targeting lipid-polymer hybrid NPs fabrication; the surface properties and stability of the hybrid NPs were systematically investigated, which confirmed that the hybrid NPs consisted of a poly (lactide-co-glycolide) core with ∼90% surface coverage of the lipid monolayer and a ∼4.4 nm hydrated polyethylene glycol (PEG) shell. Optimization results showed that the lipid:polymer mass ratio and the lipid-PEG:lipid molar ratio could affect the size, lipid association efficiency and stability of hybrid NPs. Furthermore, a model chemotherapy drug, 10-hydroxycamptothecin, was encapsulated into hybrid NPs with a higher drug loading compared to PLGA NPs. Surface modification of the lipid layer and the PEG conjugated targeting ligand did not affect their drug release kinetics. Finally, the cytotoxicity and cellular uptake studies indicated that the lipid coverage and the c(RGDyk) conjugation of the hybrid NPs gained a significantly enhanced ability of cell killing and endocytosis. Our results suggested that lipid-polymer hybrid NPs prepared by the modified emulsion technique have great potential to be utilized as an engineered drug delivery system with precise control ability of surface targeting modification.

Adsorption energies of poly(ethylene oxide)-based surfactants and nanoparticles on an air-water surface.

PubMed

Zell, Zachary A; Isa, Lucio; Ilg, Patrick; Leal, L Gary; Squires, Todd M

2014-01-14

The self-assembly of polymer-based surfactants and nanoparticles on fluid-fluid interfaces is central to many applications, including dispersion stabilization, creation of novel 2D materials, and surface patterning. Very often these processes involve compressing interfacial monolayers of particles or polymers to obtain a desired material microstructure. At high surface pressures, however, even highly interfacially active objects can desorb from the interface. Methods of directly measuring the energy which keeps the polymer or particles bound to the interface (adsorption/desorption energies) are therefore of high interest for these processes. Moreover, though a geometric description linking adsorption energy and wetting properties through the definition of a contact angle can be established for rigid nano- or microparticles, such a description breaks down for deformable or aggregating objects. Here, we demonstrate a technique to quantify desorption energies directly, by comparing surface pressure-density compression measurements using a Wilhelmy plate and a custom-microfabricated deflection tensiometer. We focus on poly(ethylene oxide)-based polymers and nanoparticles. For PEO-based homo- and copolymers, the adsorption energy of PEO chains scales linearly with molecular weight and can be tuned by changing the subphase composition. Moreover, the desorption surface pressure of PEO-stabilized nanoparticles corresponds to the saturation surface pressure for spontaneously adsorbed monolayers, yielding trapping energies of ∼10(3) k(B)T.

ATRP-based synthesis and characterization of light-responsive coatings for transdermal delivery systems

PubMed Central

Pauly, Anja C; Schöller, Katrin; Baumann, Lukas; Rossi, René M; Dustmann, Kathrin; Ziener, Ulrich; de Courten, Damien; Wolf, Martin; Boesel, Luciano F; Scherer, Lukas J

2015-01-01

The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET–ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing. PMID:27877791

ATRP-based synthesis and characterization of light-responsive coatings for transdermal delivery systems

NASA Astrophysics Data System (ADS)

Pauly, Anja C.; Schöller, Katrin; Baumann, Lukas; Rossi, René M.; Dustmann, Kathrin; Ziener, Ulrich; de Courten, Damien; Wolf, Martin; Boesel, Luciano F.; Scherer, Lukas J.

2015-06-01

The grafting of poly(hydroxyethylmethacrylate) on polymeric porous membranes via atom transfer radical polymerization (ATRP) and subsequent modification with a photo-responsive spiropyran derivative is described. This method leads to photo-responsive membranes with desirable properties such as light-controlled permeability changes, exceptional photo-stability and repeatability of the photo-responsive switching. Conventional track etched polyester membranes were first treated with plasma polymer coating introducing anchoring groups, which allowed the attachment of ATRP-initiator molecules on the membrane surface. Surface initiated ARGET-ATRP of hydroxyethylmethacrylate (where ARGET stands for activator regenerated by electron transfer) leads to a membrane covered with a polymer layer, whereas the controlled polymerization procedure allows good control over the thickness of the polymer layer in respect to the polymerization conditions. Therefore, the final permeability of the membranes could be tailored by choice of pore diameter of the initial membranes, applied monomer concentration or polymerization time. Moreover a remarkable switch in permeability (more than 1000%) upon irradiation with UV-light could be achieved. These properties enable possible applications in the field of transdermal drug delivery, filtration, or sensing.

On-surface synthesis: a promising strategy toward the encapsulation of air unstable ultra-thin 2D materials.

PubMed

Li, Qiang; Zhao, Yinghe; Guo, Jiyuan; Zhou, Qionghua; Chen, Qian; Wang, Jinlan

2018-02-22

2D black phosphorus (BP) and transition metal chalcogenides (TMCs) have beneficial electronic, optical, and physical properties at the few-layer limit. However, irreversible degradation of exfoliated or chemical vapor deposition-grown ultrathin BP and TMCs like GaSe via oxidation under ambient conditions limits their applications. Herein, the on-surface growth of an oxidation-resistant 2D thin film of a metal coordination polymer is demonstrated by multiscale simulations. We show that the preparation of such heterostructures can be conducted in solution, in which pristine BP and GaSe present better stability than in an air environment. Our calculations reveal that the interaction between the polymer layer and 2D materials is dominated by van der Waals forces; thus, the electronic properties of pristine BP and GaSe are well preserved. Meanwhile, the isolation from oxygen and water can be achieved by monolayer polymers, due to the nature of their close-packed layers. Our facile strategy for enhancing the environmental stability of ultrathin materials is expected to accelerate efforts to implement 2D materials in electronic and optoelectronic applications.

Influence of cationic lipid concentration on properties of lipid-polymer hybrid nanospheres for gene delivery.

PubMed

Bose, Rajendran J C; Arai, Yoshie; Ahn, Jong Chan; Park, Hansoo; Lee, Soo-Hong

2015-01-01

Nanoparticles have been widely used for nonviral gene delivery. Recently, cationic hybrid nanoparticles consisting of two different materials were suggested as a promising delivery vehicle. In this study, nanospheres with a poly(D,L-lactic-co-glycolic acid) (PLGA) core and cationic lipid shell were prepared, and the effect of cationic lipid concentrations on the properties of lipid polymer hybrid nanocarriers investigated. Lipid-polymer hybrid nanospheres (LPHNSs) were fabricated by the emulsion-solvent evaporation method using different concentrations of cationic lipids and characterized for size, surface charge, stability, plasmid DNA-binding capacity, cytotoxicity, and transfection efficiency. All LPHNSs had narrow size distribution with positive surface charges (ζ-potential 52-60 mV), and showed excellent plasmid DNA-binding capacity. In vitro cytotoxicity measurements with HEK293T, HeLa, HaCaT, and HepG2 cells also showed that LPHNSs exhibited less cytotoxicity than conventional transfection agents, such as Lipofectamine and polyethyleneimine-PLGA. As cationic lipid concentrations increased, the particle size of LPHNSs decreased while their ζ-potential increased. In addition, the in vitro transfection efficiency of LPHNSs increased as lipid concentration increased.

The Role of Nanofillers in Polymer Nanocomposites

NASA Astrophysics Data System (ADS)

Xu, Di

Polymer nanocomposites have been widely used in many fields. By introducing nanoparticles as fillers, researchers are able to get reinforced materials and new materials with novel properties, such as stronger mechanics, enhanced optical properties and improved conductivity. Though experimental techniques have rapidly advanced to enable better control of materials at atomic level, there is still a lack of a fundamental understanding of the dynamics and structure-properties relations in polymer nanocomposites. In this thesis, we use computer simulations to study the molecular structure and connections between microstate to macro properties of a variety of nanocomposites. Our goal is to understand the role of nanofillers in complex nanocomposite systems and to assist nanocomposite design. Nanoplatelet fillers, such as clays, have shown superior effects on the properties of polymer gels. We used molecular dynamic simulation to study nanoplatelet-filled composite gel system, in which short-range attraction exists between the polymer and nanoplatelet fillers. We show that the polymers and nanoplatelet fillers formed organic-inorganic networks with nanoplatelets acting as crosslink junctions, and the network eventually percolates the system as fillers reached a critical concentration. Stress auto-correlation and step-strain test were applied to investigate the mechanical properties; the results show the simulated composites changed from fluid-like to solid-like. The mechanical changes were consistent with the percolation transition, and gelation mechanism was therefore believed to be similar to those pure polymer physical gels. It was observed platelets aggregated into a local intercalation structure, which significantly differs from typical spherical fillers. This unique intercalation structure was examined by radial distribution function and ordering parameters. We discussed how intercalation would affect the properties of the platelet composites by comparing them with spherical fillers. Nanofillers have been widely used in polymer blends to improve the interfacial compatibility of otherwise immiscible polymers. In the second system, we investigated the interfacial behavior of binary polymer blends with different types of fillers. The interfacial tension and shear resistance were studied as a function of filler-polymer interaction, filler concentration and species of fillers. We found filler-polymer interaction is the key factor to improve the interfacial compatibility. The results show that nanofillers reduce both interfacial tension and interfacial slip at strong filler-polymer interaction. The effects of nanofillers however differ significantly from each other by their shapes. We analyzed the structure of nanofillers at the interface and their effects on the interfacial behaviors. The self-assembly of polymers into a columnar structure, while subject to a thin film environment, provides an economic route to fabricate polymer solar cell (PSC) with high conversion efficiency. In our work, we showed that two immiscible polymer segregates into to a percolating columnar structure when confined to a thin film. By adding nanofillers, with specific functionality, we can template the segregation of nanofillers to the polymer-polymer interface. We prove this process is surface tension driven and is a result that is particular for thin film geometries, where the thickness is under critical value. The results provide a theoretical basis for the column structure forming in a self-assembled PSC system, and can help to select polymer candidates that optimize PSC efficiency. These studies serve as theoretical guideline for engineering novel nanocomposites, and could lead to the design of materials with new and improved properties.

New strategy for design and fabrication of polymer hydrogel with tunable porosity as artificial corneal skirt.

PubMed

Cao, Danfeng; Zhang, Yingchao; Cui, Zhanchen; Du, Yuanyuan; Shi, Zuosen

2017-01-01

In order to obtain an ideal material using for artificial corneal skirt, a porous polymer hydrogel containing 2-hydroxyethyl methacrylate (HEMA), trimethylolpropane triacrylate (TMPTA) and butyl acrylate was prepared through one-step radical polymerization method and the usage of CaCO 3 whisker as porogen. The physical-chemical properties of the fabricated polymer hydrogel can be adjusted by CaCO 3 whisker content, such as pore size, porosity, water content of materials and surface topography. Then a series of cell biology experiments of human corneal fibroblasts (HCFs) were carried out to evaluate its properties as an artificial corneal skirt, such as the adhesion of cells on the materials with different pore size and porosity, the apoptosis on materials with different characteristics, the distribution of the cells on the material surface. The results revealed that high porosity not only could improve water content of hydrogel, but also strengthen the adhesion of HCFs on hydrogel. In addition, high porosity hydrogel with the whisker shape of pores showed much elongate spindle-like morphology than those low porosity hydrogels. MTT assay certified that the resulted polymer hydrogel material possessed excellent biocompatibility and was suitable for HCFs growing, making it promising for being developed as artificial corneal skirt. Copyright © 2016 Elsevier B.V. All rights reserved.

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennett, William R.

2007-01-01

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

Fabrication and characterization of medical grade polyurethane composite catheters for near-infrared imaging.

PubMed

Stevenson, André T; Reese, Laura M; Hill, Tanner K; McGuire, Jeffrey; Mohs, Aaron M; Shekhar, Raj; Bickford, Lissett R; Whittington, Abby R

2015-06-01

Peripherally inserted central catheters (PICCs) are hollow polymeric tubes that transport nutrients, blood and medications to neonates. To determine proper PICC placement, frequent X-ray imaging of neonates is performed. Because X-rays pose severe health risks to neonates, safer alternatives are needed. We hypothesize that near infrared (NIR) polymer composites can be fabricated into catheters by incorporating a fluorescent dye (IRDye 800CW) and visualized using NIR imaging. To fabricate catheters, polymer and dye are dry mixed and pressed, sectioned, and extruded to produce hollow tubes. We analyzed surface roughness, stiffness, dye retention, NIR contrast intensity, and biocompatibility. The extrusion process did not significantly alter the mechanical properties of the polymer composites. Over a period of 23 days, only 6.35 ± 5.08% dye leached out of catheters. The addition of 0.025 wt% dye resulted in a 14-fold contrast enhancement producing clear PICC images at 1 cm under a tissue equivalent. The addition of IRDye 800CW did not alter the biocompatibility of the polymer and did not increase adhesion of cells to the surface. We successfully demonstrated that catheters can be imaged without the use of harmful radiation and still maintain the same properties as the unaltered medical grade equivalent. Copyright © 2015 Elsevier Ltd. All rights reserved.

Surface modification of silicon wafer by grafting zwitterionic polymers to improve its antifouling property

NASA Astrophysics Data System (ADS)

Sun, Yunlong; Chen, Changlin; Xu, Heng; Lei, Kun; Xu, Guanzhe; Zhao, Li; Lang, Meidong

2017-10-01

Silicon (111) wafer was modified by triethoxyvinylsilane containing double bond as an intermedium, and then P4VP (polymer 4-vinyl pyridine) brush was "grafted" onto the surface of silicon wafer containing reactive double bonds by adopting the "grafting from" way and Si-P4VP substrate (silicon wafer grafted by P4VP) was obtained. Finally, P4VP brush of Si-P4VP substrate was modified by 1,3-propanesulfonate fully to obtain P4VP-psl brush (zwitterionic polypyridinium salt) and the functional Si-P4VP-psl substrate (silicon wafer grafted by zwitterionic polypyridinium salt based on polymer 4-vinyl pyridine) was obtained successfully. The antifouling property of the silicon wafer, the Si-P4VP substrate and the Si-P4VP-psl substrate was investigated by using bovine serum albumin, mononuclear macrophages (RAW 264.7) and Escherichia coli (E. coli) ATTC25922 as model bacterium. The results showed that compared with the blank sample-silicon wafer, the Si-P4VP-psl substrate had excellent anti-adhesion ability against bovine serum albumin, cells and bacterium, due to zwitterionic P4VP-psl brush (polymer 4-vinyl pyridine salt) having special functionality like antifouling ability on biomaterial field.

The effects of polymer carrier, hot melt extrusion process and downstream processing parameters on the moisture sorption properties of amorphous solid dispersions.

PubMed

Feng, Xin; Vo, Anh; Patil, Hemlata; Tiwari, Roshan V; Alshetaili, Abdullah S; Pimparade, Manjeet B; Repka, Michael A

2016-05-01

The aim of this study was to evaluate the effect of polymer carrier, hot melt extrusion and downstream processing parameters on the water uptake properties of amorphous solid dispersions. Three polymers and a model drug were used to prepare amorphous solid dispersions utilizing the hot melt extrusion technology. The sorption-desorption isotherms of solid dispersions and their physical mixtures were measured by the dynamic vapour sorption system, and the effects of polymer hydrophobicity, hygroscopicity, molecular weight and the hot melt extrusion process were investigated. Fourier transform infrared (FTIR) imaging was performed to understand the phase separation driven by the moisture. Solid dispersions with polymeric carriers with lower hydrophilicity, hygroscopicity and higher molecular weight could sorb less moisture under the high relative humidity (RH) conditions. The water uptake ability of polymer-drug solid dispersion systems were decreased compared with the physical mixture after hot melt extrusion, which might be due to the decreased surface area and porosity. The FTIR imaging indicated that the homogeneity of the drug molecularly dispersed within the polymer matrix was changed after exposure to high RH. Understanding the effect of formulation and processing on the moisture sorption properties of solid dispersions is essential for the development of drug products with desired physical and chemical stability. © 2015 Royal Pharmaceutical Society.

Porous organic polymers with different pore structures for sensitive solid-phase microextraction of environmental organic pollutants.

PubMed

Huang, Zhoubing; Liu, Shuqin; Xu, Jianqiao; Yin, Li; Zheng, Juan; Zhou, Ningbo; Ouyang, Gangfeng

2017-10-09

Adsorption capacity is the major sensitivity-limited factor in solid-phase microextraction. Due to its light-weight properties, large specific surface area and high porosity, especially tunable pore structures, the utilization of porous organic polymers as solid-phase microextraction adsorbents has attracting researchers' attentions. However, these works mostly concentrated on the utilization of specific porous organic polymers for preparing high-performance solid-phase microextraction coatings. The relationship between pore structures and adsorption performance of the porous organic polymers still remain unclear. Herein, three porous organic polymers with similar properties but different pore distributions were prepared by condensation polymerization reaction of phloroglucinol and terephthalaldehyde, which were fabricated as solid-phase microextraction coatings subsequently. The adsorption capacity of the porous organic polymers-coated fibers were evaluated by using benzene and its derivatives (i.e.,benzene, toluene, ethylbenzene and m-xylene) and polycyclic aromatic hydrocarbons as the target analytes. The results showed that the different adsorption performance of these porous organic polymers was mainly caused by their different pore volumes instead of their surface areas or pore sizes. Finally, the proposed method by using the mesoporous organic polymer coating was successfully applied to the determination of benzene and its derivatives in environmental water samples. As for analytical performance, high pre-concentration factors (74-2984), satisfactory relative recoveries (94.5 ± 18.5-116.9 ± 12.5%), intraday precision (2.44-5.34%), inter-day precision (4.62-7.02%), low limit of detections (LODs, 0.10-0.29 ng L -1 ) and limit of quantifications (LOQs, 0.33-0.96 ng L -1 ) were achieved under the optimal conditions. This study provides an important idea in the rational design of porous organic polymers for solid-phase microextraction or other adsorption applications. Copyright © 2017 Elsevier B.V. All rights reserved.