Content Of Polar Groups Research Articles

Effect of Surface Modification on Mechanical and Tribological Performance of Poly-p-phenylenebenzobisoxazole Fiber-Reinforced Polyimide Composite

This work examined the effect of coupling agent surface modification of Poly-p-phenylenebenzobisoxazole (PBO) fibers on mechanical and tribological performance of PBO fiber-reinforced thermoplastic polyimide (PBO/PI) composites. The results show that tensile strength and flexural strength are largely improved by coupling agent treatment. Under dry sliding conditions, coupling agent treatment is effective to reduce the wear of PBO/PI composite. The principle of improvement in interfacial adhesion between PBO fiber and PI matrix after coupling agent treatment was discussed. The surface characteristics of PBO fibers were characterized by X-ray photoelectron spectroscopy (XPS). It is found that the content of polar groups on the surface of PBO fiber treated by coupling agent increases compared with the untreated fiber. The presence of polar groups is probably leading to an increment of interfacial binding force between fibers and matrix in a composite system, and accordingly enhances the mechanical and tribological properties.

Application of thiol‐ene click chemistry to preparation of functional polyethylene with high molecular weight and high polar group content: Influence of thiol structure and vinyl type on reactivity

AbstractA series of functional polyethylenes have been simply and efficiently synthesized via the combination of regioselective ethylene/5‐vinyl‐2‐norbornene (VNB) copolymerization using [PhNC(CF3)CHCO(Ph)]2TiCl2 catalyst and following ultraviolet light initiated thiol‐ene click reaction. On treatment of ethylene/VNB copolymer with different thiols including mercaptoethanol, 1‐thioglycerol, methyl mercaptoacetate, methyl mercaptopropionate, 2‐mercaptoethylamine, mercaptoacetic acid, and mercaptopropanoic acid, various polar groups have been successfully introduced into the polyethylene. Except 2‐mercaptoethylamine, the functionalizations are quite efficient with the degree of functionalization higher than 94%, which is independent of thiol structure and double bond content. The content of polar group in functional polyethylene can be tuned in a wide range of 0–30 mol %. Gel permeation chromatography profiles indicate all functional polyethylenes that have very high molecular weights (160–336 kg/mol) with homogeneous formation. Besides, systematic investigation of the influence of vinyl type and thiol structure on reactivity has been also carried out. By treatment of mercaptoethanol with different copolymers (ethylene/VNB, ethylene/5‐ethylidene‐2‐norbornene, and ethylene/dicyclopentadiene copolymer), the order of vinyl reactivity can be summarized as terminal > internal > cyclic double bond. For different thiols, the reactivity has the sequence of SHCH2COOH > SHCH2COOCH3 > SHCH2CH2COOH > SHCH2CH2COOCH3 > SHCH2CH(OH)CH2OH > SHCH2CH2OH > SHCH2CH2NH2, which is depended on the solubility and the electron‐withdrawing inductive effect of polar group. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Developing criteria for the recovery of ionic liquids from aqueous phase by adsorption with activated carbon

Adsorption with activated carbons (ACs) has been recently reported as an affordable environmental application to remove and recover ionic liquids (ILs) from water streams. In this work, an extensive analysis of the separation of imidazolium-based ILs from aqueous solution, based on adsorption equilibrium experiments at 308K, has been performed. The study includes five commercial and four modified ACs, with a wide variety of structural and chemical properties, a carbon black and also two inorganic adsorbents. The materials tested were characterized by several techniques in order to establish the role of the porous structure and chemical surface on their adsorption capacities. We found that the microporous ACs with low concentration of polar groups in their surface are the best candidates for adsorption of hydrophobic ILs, reaching uptakes of up to 1g of IL per gram of adsorbent. The influence of both cation and anion on the adsorption process was analyzed from the adsorption isotherms of 27 different ILs. The dependence of the adsorption uptake with the chemical structure of the ILs was explained by mean of the quantum-chemical COSMO-RS model, which provides information of the intermolecular interactions between the IL adsorbate and the AC adsorbent. As a result, some insight into the adsorbent modifications needed for improving of the adsorption of specific ILs were achieved and successfully applied to the adsorption of hydrophilic ILs by oxidized ACs.In addition, a procedure for regenerating the exhausted adsorbent and recovering the IL by acetone extraction was validated upon successive adsorption–desorption cycles with two commercial ACs. Finally, the acetone was separated by atmospheric distillation, being the IL recovered without structural modification.

A facile and green preparation of poly(glycidyl methacrylate) coated aramide fibers

A new method is introduced to facilely and greenly prepared a coating with functional groups on the surface of aramide fibers through a polymerization using horseradish peroxidase as the catalyst. The chemical and morphological structures of the poly(glycidyl methacrylate) (PGMA) coated aramide fibers (PGMA@KF) were systemically characterized by attenuated total reflection infrared spectrometry (ATR-IR), X-ray photoelectron spectroscopy (XPS), Scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and wide angle X-ray diffraction (WAXD). Interestingly, the surface morphology and chemical composition of the PGMA@KF fibers can be controlled by adjusting the concentration of glycidyl methacrylate (GMA) for polymerization. These variations in structure between PGMA@KF and the original aramide (KF) fibers are also reflected in the macro-performance of the fibers. Compared with the KF fibers, the PGMA@KF fibers not only have dramatically increased content of polar groups, higher surface free energy, and rougher surfaces, but also show obviously increased mechanical properties, while maintaining excellent thermal resistance. For example, for PGMA@KF fibers with a compact coating of PGMA, its tenacity, energy to break, and modulus are about 23%, 19.4%, and 16.4% higher, respectively, than those of KF fibers. This attractive feature makes PGMA@KF fibers have superb advantages, compared to previous chemically modified aramide fibers in the literature. This investigation suggests that the method developed herein is an effective technique to prepare high performance organic fibers and corresponding materials.

Effect of surface modification of poly-p-phenylenebenzobisoxazole fiber with lanthanum salt on flexural and tribological properties of composite with polyimide

The effect of lanthanum (La) salt on surface treatment of poly-p-phenylenebenzobisoxazole (PBO) fiber on flexural and tribological properties of PBO fibers reinforced polyimide (PI) composites was investigated. Experimental results revealed that flexural strength and modulus were largely improved by La salt treatment. The La salt treated composite had lower friction coefficient and specific wear rate than that of untreated one under the same testing condition. The principle of improvement in interfacial adhesion between PBO fiber and PI matrix after La salt treatment was discussed. The surface characteristics of PBO fibers were characterized by X-ray photoelectron spectroscopy. It was found that the content of polar groups on the surface of PBO fiber treated by La salt increased compared with the untreated fiber. The increase in the amount of polar groups strengthened the interfacial adhesion between PBO fibers and PI matrix, and accordingly enhanced the flexural and tribological properties.

Tensile property of surface-treated poly-p-phenylenebenzobisoxazole (PBO) fiber-reinforced thermoplastic polyimide composite

The current study examined the effect of rare earth (RE) solution surface modification of poly- p-phenylenebenzobisoxazole (PBO) fibers on the tensile property of PBO fiber-reinforced thermoplastic polyimide (PBO/PI) composites. Experimental results revealed that RE surface treatment could effectively improve the interfacial adhesion between PBO fibers and PI matrix. Compared with the untreated and coupling agent-treated PBO/PI composite, the RE-treated composite had better interfacial adhesion. For RE-treated PBO/PI composites, the tensile strength and tensile modulus varied with RE concentrations, and the optimum value was obtained at 0.6 wt% of RE concentration. The fracture surface morphologies of the samples were investigated by scanning electron microscopy (SEM) to analyze the effect of various surface treatments. X-ray photoelectron spectroscopy (XPS) study of PBO fibers surface showed that the ratio of oxygen/carbon on the surface of PBO fibers was obviously increased after RE treatment, which indicated the content of polar groups on the surface of PBO fibers increased compared with the others. The increase in the amount of polar groups strengthened the interfacial adhesion between PBO fibers and PI matrix and accordingly enhanced the tensile properties.

Water transport in aluminium oxide-poly(ethylene- co-butyl acrylate) nanocomposites

Polymer composites with metal oxide nanoparticles are emerging materials for use as insulation in electrical applications. However, the extensive interfacial surfaces and the presence of polar groups on the particle surfaces make these composites susceptible to water sorption. Water sorption kinetics were studied at 23 °C and different relative humidities (18–90%) for composites based on poly(ethylene- co-butyl acrylate) and aluminium oxide (⩽12 wt.%); the latter being in three different forms: uncoated and coated with either octyltriethoxysilane or aminopropyltriethoxysilane. The equilibrium water uptake increased linearly with increasing overall concentration of polar groups on the nanoparticle surfaces. Composites with well-dispersed nanoparticles showed Fickian diffusion (constant diffusivity and invariant boundary conditions) with a diffusivity that decreased with increasing filler content; the maximum factorial decrease in diffusivity was 300 with reference to that of the pristine polymer. This effect was most pronounced for composites with accessible polar groups on the particle surfaces, suggesting that water saturation of the composites is retarded by dual water sorption. Composites that contained a sizeable fraction of large nanoparticle agglomerates showed a two-stage sorption process: a rapid process associated with the saturation of the matrix phase and a slow diffusion process due to water sorption by the large nanoparticle agglomerates.

Surface Modification of Para-Aramid Fiber by Direct Fluorination and its Effect on the Interface of Aramid/Epoxy Composites

Surface modification of a para-aramid fiber (DAFIII) was performed by direct fluorination. The properties of treated and untreated fibers were characterized and compared in detail by mechanical testing, Fourier transform infrared (FTIR) spectroscopy characterization, X-ray photoelectron spectroscopy (XPS) analysis and static contact angle measurements. The results showed that little damage of the fiber occurred after direct fluorine treatment, and the content of polar groups on the fibers surfaces were increased significantly, which resulted in a lower value of contact angle. The interlaminar shear strength (ILSS) of DAFIII fiber/epoxy composites and the tensile strength of NOL-ring specimens increased by 33% and 12%, increasing to 56.2 MPa and 2340 MPa, respectively, which indicated that the interfacial adhesion between the matrix and the aramid fiber was improved significantly by the fluorination treatment. Further tests showed that the durability of the direct fluorination treatment on the aramid fiber was also satisfactory.

Self-organization of sulfopolystyrene ionomers in solutions: Dependence on the polarity of the solution and the content of ionogenic groups in chains

The self-organization of ionomers of sulfonated polystyrene containing different amounts of SO3Na ionogenic groups (0.5, 1.35, and 2.6 mol %) in three solvents (benzene, toluene, and THF) is studied via the methods of neutron scattering. It is shown that, in toluene, ionogenic groups form “effective” chains of up to 10–20 macromolecules owing to aggregation. In benzene, chains of both the PS precursor and ionomers are surrounded by volume solvate shells in the form of ∼4-nm-dia tubes that hamper interaction between ionomers via ionogenic groups. The tendency of ionomer chains toward aggregation in benzene is enhanced as the content of polar groups in chains is increased to 2.6 mol %. The diameter of solvate shells around chains decreases to ∼1 nm, and chains associate to form denser structures. In this case, the degree of integration of macromolecules turns out to be smaller than that in toluene. In THF, the processes of solvation and structuring of PS precursor chains are well defined and compete with tendencies toward association through ionogenic groups in solutions of ionomers. The formation of developed supramolecular structures in THF is hindered by the shielding of the potentials of interaction between ion pairs because of a high dielectric constant of the solvent.

Amphiphile polydimethylsiloxane‐based networks reinforced with in situ generated silica

AbstractPolydimethylsiloxanes, side functionalized in different degrees with chloromethyl groups, were reacted with 4,4′‐bipyridyl and crosslinking occurred by the formation of ionic (bipyridinium) groups. The reactions were carried out in a silica sol–gel system, and thus, two networks were generated simultaneously: amphiphile siloxane‐organic and silica networks. The samples, processed as films, were characterized by Fourier transform infrared spectroscopy to verify the occurrence of the crosslinking reactions. Different techniques were also used to evaluate the properties: differential scanning calorimetry for emphasizing the transitions, scanning electron microscopy, and atomic force microscopy for the evaluation of the morphology and surface topography. The modification of the film surface topography, which depends on the solvent polarity, was also emphasized. The sorption capacities of the water vapors and of liquid solvents (water and chloroform) were investigated, and the obtained values proved to be a function of the polar group's content. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers

Evaluations of PP-g-GMA and PP-g-HEMA as a compatibilizer for polypropylene/clay nanocomposites

In this study, we investigated the performances of a hydroxy ethyl methacrylate grafted PP (PP-g-HEMA) and a glycidyl methacrylate grafted PP (PP-g-GMA) as compatibilizers in PP/clay nanocomposites. The compatibilizers were prepared by melt grafting with a radical initiator. Since the PP-g-MA is successfully and widely used in the PP/clay nanocomposites, we also studied three PP-g-MAs containing different amounts of MA and having different molecular weights for a comparison. PP/clay nanocomposites compatibilized by the PP-g-HEMA and the PP-g-GMA show a similar level of the clay interlayer distances with those of the PP-g-MAs. We also investigated the effect of molecular weights of the compatibilizers. In general, the compatibilizer of lower molecular weight was observed to exhibit lower performance as a compatibilizer. It is observed that an increase of polar group content in the modified PP (PP-g-HEMA, PP-g-GMA, and PP-g-MA) always accompanies the molecular weight reduction, which deteriorates the mechanical properties. Thus, we prepared the PP-g-HEMA and PP-g-GMA by incorporation of a styrene comonomer. The compatibilizers (PP-g-HEMA-co-styrene and PP-g-GMA-co-styrene) thus obtained show good performance as a compatibilizer in the PP/clay nanocomposites. We observed that the PP/clay composites containing the PP-g-HEMA-co-styrene and the PP-g-GMA-co-styrene have very well-balanced mechanical properties.

CHO Cells Adhering to Nitrogen‐Rich Plasma‐Polymerised Ethylene Exhibit High Production of a Specific Recombinant Protein

In many industrial applications, inadequate cell attachment can be a limitation, especially when serum-free media are used. Nitrogen-rich plasma-polymerised ethylene (PPE:N) exhibits high concentrations of polar groups that can help to promote the attachment of weakly adherent cell types. Tissue plasminogen activator-producing Chinese hamster ovary (CHO) cells, adapted to suspension, were grown in the presence PPE:N flakes and were found to adhere to them. The growth rate was reduced, but cell viability was enhanced and their metabolism was more efficient, with generally higher recombinant protein productivity. Finally, cell adhesion on PPE:N surfaces was found to be independent of integrins, and was probably mediated by certain non-specific interactions with the PPE:N surface.

XPS study of PBO fiber surface modified by incorporation of hydroxyl polar groups in main chains

Dihydroxy poly(p-phenylene benzobisoxazole) (DHPBO), a modified poly(p-phenylene benzoxazole) (PBO) polymer containing double hydroxyl groups in polymer chains, was synthesized by copolymerization of 4,6-diamino resorcinol dihydrochloride (DAR), purified terephthalic acid (TA) and 2,5-dihydroxyterephthalic acid (DHTA). DHPBO fibers were prepared by dry-jet wet-spinning method. The effects of hydroxyl polar groups on the surface elemental compositions of PBO fiber were investigated by X-ray photoelectron spectroscopy (XPS). The results show that the ratio of oxygen/carbon on the surface of DHPBO fibers is higher than that on the surface of PBO fibers, which indicates the content of polar groups on the surface of DHPBO fiber increase compared with PBO fiber.

Neutron study of self-organization in solutions of ionomers based on sulfonated polystyrene

Processes of self-organization of ionomers based on sulfonated PS containing ionogenic groups in the salt form (SO3Na) in chloroform have been studied by small-angle neutron scattering. At a small content of ionogenic groups SO3Na (1.35 mol %), the conformation of PS chains changes from coil-like to globular due to electrostatic interactions between them. An increase in the share of ionogenic groups to 2.6 mol % brings about the assembly of ionomer chains into a hollow spherical structure with the solvent inside. In the shell of a micelle, polar groups are densely packed and shielded from the solvent by nonpolar fragments of adjoining chains. At a low content of ionogenic groups in ionomers, two-thirds of macromolecules in solution are not incorporated in any structures. With an increase in the content of polar groups to 2.6 mol %, almost all chains are organized to small clusters—the stable pairs of macromolecules.

Oxygen and Water Vapor Barrier Properties of MMT Nanocomposites from Low Density Polyethylene or EPM with Grafted Succinic Groups

LDPE, EPM and their derivatives containing a moderate amount (0.08-1.8 by mol) of diethylsuccinate or succinic anhydryde groups were used as matrices in blending with different amount of organophilic montmorillonites and the resulting composite morphology and structure (by XRD, SEM, TEM microscopy, DSC analysis and selective solvent extraction) were studied with reference to the polar groups/MMT ratio. Exfoliated, intercalated and mixed morphologies were achieved. High concentrations of polar groups grafted to the polyolefin and montmorillonite loading not larger than 5% wt were favourable for obtaining high exfoliation degree. Particularly in the exfoliated MMT composite LDPE had lower crystallinity degree, while EPM showed increased glass transition temperature and reduced solubility in hot toluene. Moreover, oxygen and water vapor barrier property improvement was observed in films where MMT exhibits either exfoliated or intercalated morphologies. Strong interactions with the montmorillonite particle surface through the polar groups grafted to the polyolefin seems to be the basic effect responsible for the morphology and peculiar properties. A model based on the reduced mobility of the polymer located near the particle surface or inside the MMT gallery (confined phase) was proposed to explain the observed oxygen permeability reduction, the T(g) increase and solubility of poly(ethylene-ran-propylene)/MMT nanocomposites.

Oxygen and Water Vapor Barrier Properties of MMT Nanocomposites from Low Density Polyethylene or EPM with Grafted Succinic Groups

LDPE, EPM and their derivatives containing a moderate amount (0.08-1.8 by mol) of diethylsuccinate or succinic anhydryde groups were used as matrices in blending with different amount of organophilic montmorillonites and the resulting composite morphology and structure (by XRD, SEM, TEM microscopy, DSC analysis and selective solvent extraction) were studied with reference to the polar groups/MMT ratio. Exfoliated, intercalated and mixed morphologies were achieved. High concentrations of polar groups grafted to the polyolefin and montmorillonite loading not larger than 5% wt were favourable for obtaining high exfoliation degree. Particularly in the exfoliated MMT composite LDPE had lower crystallinity degree, while EPM showed increased glass transition temperature and reduced solubility in hot toluene. Moreover, oxygen and water vapor barrier property improvement was observed in films where MMT exhibits either exfoliated or intercalated morphologies. Strong interactions with the montmorillonite particle surface through the polar groups grafted to the polyolefin seems to be the basic effect responsible for the morphology and peculiar properties. A model based on the reduced mobility of the polymer located near the particle surface or inside the MMT gallery (confined phase) was proposed to explain the observed oxygen permeability reduction, the T(g) increase and solubility of poly(ethylene-ran-propylene)/MMT nanocomposites.

Improvement of Adhesion Between Liquid Crystalline Polyester Films by Plasma Treatment

Surface modification of thermotropic liquid crystalline aromatic polyester (LCP) films was carried out by low-pressure plasma treatment to improve the initial adhesion as well as the long-term adhesion reliability, a measure of durability between the LCP films used as substrates for printed circuit boards. Plasma irradiation was carried out in various plasma gases with different plasma modes such as reactive-ion-etching, and direct-plasma (DP) with pressures ranging from 6.7 Pa to 26.6 Pa. The introduction of polar groups on the film surface such as phenolic hydroxyl groups and carboxyl groups enhanced the initial adhesion by increased chemical interaction. However, if the concentration of polar groups became too high, the longterm adhesion reliability estimated by the pressure cooker test was degraded due to the acceleration of the penetration of water molecules into the interface. A large surface roughness was also effective in preventing the decrease in the long-term adhesion reliability. However, too much increase in surface roughness decreases the long-term adhesion reliability. The DP-treatment in the O2 atmosphere at a gas pressure of 6.7 Pa was found to be the best plasma condition for both the initial adhesion as well as the long-term adhesion reliability between the LCP films.

Specific features of the electret effect in two-layer polymeric films

Two-layer film corona-electrets based on low-density polyethylene and copolymers of ethylene with vinyl acetate of various brands were studied. The dependence of the electret characteristics of two-layer corona-electrets on the percentage content of polar groups in the copolymer constituting the bottom layer was analyzed. Data on thermally stimulated depolarization and thermally stimulated relaxation of the surface potential served as a basis for suggesting a mechanism of depolarization of two-layer corona-electrets.

Structure–properties relationships in clay nanocomposites based on PVDF/(ethylene–vinyl acetate) copolymer blends

The relationships between the microscopic structure and the macroscopic properties in two sets of clay nanocomposites based on polymer blends comprised of poly(vinylidene fluoride) (PVDF) and ethylene–vinyl acetate copolymer (EVAc) were examined. In nanocomposites based on a polymer blend matrix with high content of polar groups (VAc) the dispersion of polar nanoclay leads to significant enhancement in toughness and a substantial increase in viscosity. However, in nanocomposite blends based on a less polar matrix (i.e. with fewer VAc groups) it is the hydrophobic organoclay that leads to higher modulus and stronger viscoelasticity. The dispersion of nanoparticles and the mechanical response are discussed in terms of emulsifying efficiency of the clay particles in the immiscible polymer blend, an effect that largely depends on the localized interactions between the polymer groups and the clay surface modifier. The potential of nanoclays to serve as matrix sensitive structure-directing agents in tailor-made materials is demonstrated.

Study of the properties and structure of polyimide and bilayer fluoropolyimide films after space exposure on the Mir space station

Results of examination of bilayer polyimide and fluorinated polyimide films after their exposure to outer space on the Mir space station are reported. The polyimide films were screened by quartz plates during exposure. An increase in the surface energy and the work of adhesion indicate substantial hydrophilization of the open surface, as well as slight hydrophilization of the screened film surface. A difference in values of the surface energy and work of adhesion depending on the orientation of a sample relative to the direction of motion of the space station indicates that the surface properties of the outer surface of the unscreened film became anisotropic in character, with the anisotropy axis being aligned with the direction of motion of the spacecraft. The fact that the outer surface of the film has acquired anisotropic properties is corroborated by the results of study of scanning electron microscopic images and polar plots of brightness. The hydrophilization of the films indicates an increase in the concentration of polar groups. In the space environment, the degradation of the fluoropolymer surface layer and its removal under high-vacuum conditions take place. For the quartz-shielded polyimide films, the surface energy and the work of adhesion remained practically the same as for the unexposed films. It was concluded that solar radiation (μ > 200 nm) does not cause a significant decline in the properties of the polyimide film.