Rapid formation of soft hydrophilic silicone elastomer surfaces

We report on the rapid formation of hydrophilic silicone elastomer surfaces by ultraviolet/ozone (UVO) irradiation of poly(vinylmethyl siloxane) (PVMS) network films. Our results reveal that the PVMS network surfaces render hydrophilic upon only a short UVO exposure time (seconds to a few minutes). We also provide evidence that the brief UVO irradiation treatment does not cause dramatic changes in the surface modulus of the PVMS network. We compare the rate of formation of hydrophilic silicone elastomer surfaces made of PVMS to those of model poly(dimethyl siloxane) (PDMS) and commercial-grade PDMS (Sylgard-184). We find that relative to PVMS, 20 times longer UVO treatment times are needed to oxidize the PDMS network surfaces in order to achieve a comparable density of surface-bound hydrophilic moieties. The longer UVO treatment times for PDMS are in turn responsible for the dramatic increase in surface modulus of UVO treated PDMS, relative to PVMS. We also study the formation of self-assembled monolayers (SAMs) made of semifluorinated organosilane precursors on the PVMS-UVO and PDMS-UVO network surfaces. By tuning the UVO treatment times and by utilizing mono- and tri-functional organosilanes we find that while mono-functionalized organosilanes attach directly to the substrate, SAMs of tri-functionalized organosilanes form in-plane networks on the underlying UVO-modified silicone elastomer surface, even with only short UVO exposure times.     

Access to new carbohydrate-functionalized polylactides via organocatalyzed ring-opening polymerization

The 4-dimethylaminopyridine (DMAP) catalyzed ring-opening polymerization of lactide using various carbohydrate initiators has been assessed for the functionalization of polylactide. Selectively protected glucose derivatives bearing a free primary alcohol (Glc-1r) and a free secondary alcohol (Glc-2r), glucose and cyclodextrin diol derivatives (Glc-diol and CD-diol), methyl-α-d-glucopyranoside (Glc-Me) and native β-cyclodextrin (CD) were used as initiators. According to the solubility of the carbohydrate derivative, the polymerizations were conducted in chlorinated solvents and in the bulk. Relatively narrow distributions are obtained in high yields in the absence of side reactions, affording a 100% functionalization efficiency. The catalytic synthesis of new carbohydrate link-functionalized polylactides and carbohydrate core star polylactides is reported.     

Comparison with as-grown and microwave modified carbon nanotubes to removal aqueous bisphenol A

This study utilized carbon nanotubes (CNTs) to remove bisphenol A (BPA) from aqueous solution. The surfaces of CNTs were modified by SOCl₂/NH₄OH under microwave irradiation. The surface characteristics of as-grown and modified CNTs were analyzed by measuring zeta potential, and using a scanning electron microscope, a surface area analyzer and a Fourier transform infrared spectroscope. The specific surface area of modified CNTs exceeded that of as-grown CNTs. The pH_iep values of as-grown CNTs and modified CNTs were determined to be 4.3 and 6.5, respectively. Some amine functionalities were formed on the surface of modified CNTs; therefore, the surface of the modified CNTs contained more positive charges than that of the as-grown CNTs. The adsorption kinetics were examined using pseudo first- and second-order models, intraparticle diffusion and Bangham's models. The equilibrium data were simulated using Langmuir, Freundlich, Dubinin and Radushkevich (D-R) and Temkin isotherms. The results reveal that the pseudo second-order model and Langmuir isotherm fit the kinetics and equilibrium data, respectively. The adsorption capacity of BPA on the surface of CNTs fluctuates very little with pH in the range of 3-9, suggesting the high stability of CNTs as an adsorbent for BPA over a rather wide pH range. The values of ΔH⁰ and ΔS⁰ were calculated to be − 11.7 kJ/mol and 46.1 J/mol, respectively. The isotherm and thermodynamic simulations indicate that the adsorption of BPA onto as-grown CNTs proceeds by physisorption process.     

Nitrogen and hydrogen adsorption of activated carbon fibers modified by fluorination

In this study, activated carbon fibers (ACFs) were surface modified with fluorine and mixed oxygen and fluorine gas to investigate the relationship between changes in surface properties by nitrogen and hydrogen adsorption capacity. The changes in surface properties of modified activated carbon fibers were investigated using X-ray photoelectron spectroscopy (XPS) and compared before and after surface treatment. The specific surface area and pore structures were characterized by the nitrogen adsorption isotherm at liquid nitrogen temperature. Hydrogen adsorption isotherms were obtained at 77 K and 1 bar by a volumetric method. The hydrogen adsorption capacity of fluorinated activated carbon fibers was the smallest of all samples. However, the bulk density in this sample was largest. This result could be explained by virial coefficients. The interaction of hydrogen-surface carbon increased with fluorination as the first virial coefficient. Also, the best fit adsorption model was found to explain the adsorption mechanism using a nonlinear curve fit. According to the goodness-of-fit, the Langmuir–Freundlich isotherm model was in good agreement with experimental data from this study.     

Electron beam modification of filled fluorocarbon rubber

The effect of electron beam irradiation on the properties of carbon black‐, silica‐, and clay‐filled fluorocarbon rubber has been studied over a range of radiation doses, loadings, and nature of the fillers. Compared to the unfilled irradiated rubber, the tensile strength and modulus improve with a decrease in the particle size of the carbon black filler. Similar improvement in these properties is observed with an increase in both the radiation dose and the amount of the filler upto a certain level. The dynamic mechanical analysis reveal an increased glass transition temperature (T_g), a reduced value of the mechanical loss factor at T_g. and an enhanced dynamic storage modulus for the filled samples. The results are explained with the help of sol‐gel analysis and volume fraction of rubber. It is observed that higher reinforcement in the case of the filled vulcanizate is obtained by electron beam modification, as compared to that using the conventional curing system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 2016–2025, 2000     

Modification of the surface reactivity of Cu-MFI during chemisorption and transformation of the reagents in the selective reduction of NO with propane and O2

The steady-and unsteady-state catalytic behaviour of Cu-MFI in the conversion of propane and NO in the presence of O₂ is reported, showing how the chemisorption and transformation of reactants may influence the surface reactivity. Various effects were observed: (i) a change in the surface reactivity and kinetics in going from low to high concentrations of NO or propane, (ii) the transformation of NO to N₂ and N₂O promoted at low temperature (250°C) by oxygen in the absence of hydrocarbon, (iii) the influence of NO over the surface reactivity of the catalyst in the conversion of propane and (iv) the influence of surface precoverage with oxidized nitrogen oxides (N_xO_y) or carboxylate species on the catalyst transient reactivity in the reduction of NO to N₂. In particular, Cu-MFI is initially more active when oxidized nitrogen oxides are present, suggesting that the active intermediate in the reduction of NO with propane is a complex formed by the reaction of nitrate with activated hydrocarbon. It is shown, however, that strongly bound oxidized nitrogen oxides may have also additional effects on the surface reactivity: (i) can promote the conversion of NO to N₂ and N₂O in transient conditions and (ii) can give a partial inhibition of the surface reactivity blocking copper ions due to their strong chemisorption. Furthermore, it is shown that NO reacts faster with oxygen than hydrocarbon forming N_xO_y species which are then the oxidizing agent for the hydrocarbon. It is thus suggested that the surface reactivity of Cu-MFI in the reduction of NO with propane/oxygen depends on the surface population of nitrogen oxide adspecies which influence not only the surface reactivity, but also the pathway of hydrocarbon oxidation.     

Homogeneous preparation of polyamidoamine grafted silica gels and their adsorption properties as Au3+ adsorbents

A series of low generation dendrimer polyamidoamine grafted silica gels (named SiO₂-G1.0, SiO₂-G2.0, SiO₂-G3.0) were synthesized via the homogeneous route. The new materials were characterized by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), thermal analysis, pore and surface area analysis, X-ray diffraction analysis (XRD) and elemental analysis. The adsorption properties of the three products for Au³⁺ were studied by batch methods. The adsorbents prepared via the homogeneous route showed higher adsorption capacities than those via the heterogeneous route. The maximum adsorption capacities for the three could reach up to 1.48, 2.45, and 2.21 mmol g⁻¹, respectively.     

Synthesis of a soluble functionalized-silica by the hydrolysis and condensation of organotrialkoxysilanes bearing (β-hydroxy) tertiary amine groups with tetraethoxysilane

The hydrolytic condensation of organotrialkoxysilanes containing (β-hydroxy) tertiary amine groups generates a significant fraction of intramolecular cycles and leads to the formation of closed structures. The aim of this study was to investigate if their co-condensation with a tetraalkoxy silane would take place by predominant intramolecular cyclization steps, eventually leading to functionalized silicas that can be dissolved in appropriate solvents. Co-condensation of tetraethoxysilane (TEOS) with the organotrialkoxysilane derived from the reaction of N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane with phenyl glycidyl ether, was performed in the presence of HCOOH using a thermal cycle attaining 150 °C. For TEOS molar fractions lower than 0.7, soluble functionalized-silicas containing up to about 25 wt% of inorganic silica chemically bonded to bulky organic groups, could be synthesized. The glass transition temperature of the organic part was close to 25 °C; it was inferred that the inorganic part was vitrified at the maximum temperature of the selected thermal cycle (150 °C). Most of the Si atoms supplied by the trialkoxysilane were present in fully condensed structures (T³), while those supplied by TEOS were present mostly as Q³ and Q⁴ structures. These soluble functionalized-silicas may be used to introduce silica as a reinforcement of a polymer network. An example is shown, using an epoxy-diamine formulation. The equivalent of 10 wt% silica could be incorporated to the final network at the expense of a reduction of 26 °C in its glass transition temperature.     

氟碳树脂的合成及有机硅改性

以偶氮二异丁腈为引发剂,甲基异丁基甲酮为溶剂,将氟碳单体与甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯等单体进行溶液聚合得到氟碳树脂共聚物。当氟碳单体质量分数较低(5％)时,加入质量分数为2％～8％的有机硅烷偶联剂单体,制得有机硅改性氟碳树脂共聚物。性能测试结果表明：该有机硅改性共聚物具有硬度高、耐水、耐碱、耐溶剂、表面自洁及耐沾污等优良性能。有机硅改性不但提高了氟碳树脂的性能,而且降低了成本,为其工业化生产和制备有机硅改性全氟碳涂料创造了条件。     

Synthesis of functionalized SBA-15 with ordered large pore size and its adsorption properties of BSA

SBA-15, mesoporous material, is a very excellent candidate for drug delivery system because its pore size is easy to control according to synthesis conditions and the presence of swelling agent. In this study, a known swelling agent, 1,3,5-trimethylbenzene (TMB), was used to increase the pore size with increased aging temperature and prolonged aging time. Furthermore, 3-aminopropyltriethoxysilane (APTES) was incorporated on SBA-15 surface via post synthesis method to separate protein effectively. The samples were characterized by X-ray diffraction (XRD), nitrogen adsorption and desorption analyses, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier Transform Infrared (FT-IR). Adsorption capacity increased with temperature at the isoelectric point (pI) of bovine serum albumin (BSA) regardless of the pore size of SBA-15 samples. Release studies were carried out in the range of pH from neutral to basic solution on unmodified and amine-modified samples. In addition, the adsorption mechanism was investigated by employing the pseudo-first order, pseudo-second order, and intraparticle diffusion models.     

Electrochemical modification of glassy carbon electrode by poly-4-nitroaniline and its application for determination of copper(II)

Electrochemical modification of glassy carbon (GC) electrode by poly-4-nitroaniline (P4NA), electrochemical reduction of P4NA and applicability of electrode modified in this way for determination of copper(II) (Cu(II)) is reported in this study. Electrochemical surface modification was performed by cyclic voltammetry in the potential range between +0.9 V and +1.4 V vs. Ag/Ag⁺ (in 10 mM AgNO₃) at the scan rate of 100 mV/s by 100 cycles in non-aqueous media. In order to provide electrochemical reduction of nitro groups on the P4NA-modified GC electrode surface (P4NA/GC), the cyclic voltammograms inducing/evidencing the reduction of nitro groups were performed in the potential range between −0.1 V and −0.8 V vs. Ag/AgCl/(sat.KCl) at the scan rate of 100 mV/s. The reduced P4NA/GC surfaces (Reduced-P4NA/GC) were treated with aqueous solution of nitrilotriacetic acid. The sensitivity of GC electrode modified in described way towards Cu(II) was investigated in Britton-Robinson buffer solution, pH 5.0. The potentiometric generic pulse technique was applied as innovative electrochemical method for detection of analytical signal. It was shown that GC electrodes modified in here described way will be suitable for the determination of Cu(II) in technological waste water and/or some other solutions containing Cu(II) ions.     

Improvement of CO2 adsorption on ZIF-8 crystals modified by enhancing basicity of surface

The imidazolate framework ZIF-8 samples were modified separately by using ammonia impregnation and thermal treatment in atmosphere of N₂ or H₂ in order to improve its adsorption property toward CO₂, and the modified samples A-ZIF-8, N-ZIF-8 and H-ZIF-8 were correspondingly available. The modified ZIF-8 samples were characterized, and the surface chemical properties of the ZIF-8 samples were determined separately by FTIR, CO₂-TPD, NH₃-TPD and H₂O-TPD. The isotherms of CO₂ on the modified ZIF-8 samples were measured. Results showed that after surface modification, the total amounts of basicity of the modified samples significantly increased, and followed the order: A-ZIF-8>H-ZIF-8>N-ZIF-8>O-ZIF-8. The uptakes of CO₂ increased proportionally with the basic groups on the surfaces of the ZIF-8 samples due to CO₂ being an acidic molecule. As a consequence of that, the CO₂ adsorption capacity of the samples followed the order: A-ZIF-8>H-ZIF-8>N-ZIF-8>O-ZIF-8. The amount adsorbed of CO₂ on the modified ZIF-8 sample by ammonia impregnation is the highest, having an increase.     

Synthesis and application of polyethylene-based functionalized hyperbranched polymers

Polyethylene is one of the largest volume commodity polymers, with excellent physical and chemical properties. Polyethylene-based functionalized hyperbranched polymers are newly developed materials with unique structures and properties. Their architecturally complex structure – topology, composition and functionality – may be designed for different applications, with reduction of complexity and cost in preparation. This review focuses on the synthesis strategies and applications of polyethylene-based functionalized hyperbranched polymers.     

Surface Modification and Vapor-Induced Response of Poly(Vinylidene Fluoride)/Carbon Black Composite Conductive Thin Films

A novel polymer sensing film was prepared by filling carbon blacks (CBs) into alkali-treated poly(vinylidene fluoride) (PVDF) matrices under ultrasonication. The microstructure, thermoproperties and crystalline behavior were investigated by FTIR, WAXD and DSC. The percolation behavior and vapor-induced response were examined, and the relationship between structure and response was elucidated. The results indicated that the reaction occurred in non-crystal regions, and had no effect on the crystal region and the main chains. The introduction of some functional groups and the aggregate behavior change in the non-crystal regions altered the interaction between polymer and solvent molecules, and further affected vapor response.     

Adsorption of vitamin B12 on ordered mesoporous carbons coated with PMMA

Ordered mesoporous carbons CMK-3 and CMK-1 were prepared from SBA-15 and MCM-48 materials with pore diameters 3.9 nm and 2.7 nm, respectively. When both mesoporous carbons were coated with about 10 wt.% poly(methyl methacrylate) (PMMA), the pore diameters decreased from 3.9 nm to 3.4 nm for CMK-3 and from 2.7 nm to 2.5 nm for CMK-1. These mesoporous carbons containing about 10 wt.% PMMA were studied as adsorbents of Vitamin B 12 (VB12) from water solutions, and their performances were compared with that of pristine CMK-3, CMK-1. Compared with CMK-1, CMK-3 showed higher vitamin B12 adsorption due to a larger mesopore volume, a higher BET surface and a larger pore diameter. After coated with PMMA, both mesoporous carbons showed higher adsorption capacity than pristine materials. The adsorption properties were influenced by the pore structure and surface properties of mesoporous carbons.     

Confined photo-catalytic oxidation: a fast surface hydrophilic modification method for polymeric materials

When a very thin persulfate salt aqueous solution layer (μm) was sandwiched between two polymer films and strong UV light irradiated the assembly from the side transparent to UV light, a fast surface hydrophilic modification method for most of commercial polymeric materials was developed. For example, irradiating for 90 s and using 30 wt% ammonium persulfate, the static surface water contact angles of polymeric substrates decreased from 100 to 44° for LDPE, from 107 to 34° for HDPE, and from 73 to 15° for PET. The increases in surface hydrophilicity came from the formation of a sulfate salt group (SO₄⁻NH₄⁺)-ionized surface, which was characterized by XPS and ATR-FTIR. The surface topography of the modified polymer substrates were observed by SEM and AFM, and no visible etching effect to original surface were found. A possible reaction model named by ‘confined photo-catalytic oxidation’ was put forward to interpret the above results.     

ON THE ASYMMETRY OF ADSORPTION AND DESORPTION IN MICROPOROUS SOLIDS

We have presented in this paper a theory to explain the asymmetry of the adsorption curve and the desorption curve in microporous solids by taking into account the surface mass action process at the pore mouth of the micropore. Effects of concentration and temperature are particularly investigated. The difference between the activation energy for desorption and that for micropore diffusion has been found to have a strong effect on this asymmetry.     

Modification of carbon nanotubes with well-controlled fluorescent styrene-based polymers using the Diels-Alder reaction

A simple and single-step “grafting to” approach based on the Diels-Alder (DA) reaction is described to functionalize multi-wall carbon nanotubes (MWCNTs) with polystyrene (PSt). Thus, several fluorescent and furfuryl functionalized PSts, synthesized by the atom transfer radical polymerization (ATRP) of styrene, furfuryl methacrylate and low proportion of a fluorescent monomer, were covalently attached onto the pristine nanotubes. Furfuryl (diene) groups allowed the chemical attachment of the PSt polymer onto the as-synthesized MWCNTs by a DA reaction. On the other hand, the incorporation of fluorescent groups in the polymer has two main advantages. It permits to determine the attachment of the polymer onto the nanotubes and, in further applications, it will allow to follow the dispersion of these modified MWCNTs in a matrix. The efficiency of the functionalization was verified by FTIR, Raman spectroscopy, TEM, AFM and fluorescence techniques.     

Hydrophobisation of active carbon surface and effect on the adsorption of water

A technique of surface hydrophobisation has been applied to two microporous carbonaceous adsorbents. A granular active carbon and an activated carbon fibre, both formerly chemically treated in order they preferentially present hydroxyl surface functions, were modified by action of vinyltrimethoxysilane (vtmos) in liquid phase. The resulting samples were characterised using sorption of nitrogen, FTIR, XPS and ²⁹Si MAS-NMR spectroscopy, and elemental analysis. Their stability and heat treatment have also been investigated through thermal analysis.The efficiency of the hydrophobisation treatment was evaluated by static adsorption of water vapour and vapours of chlorinated volatile organic compounds (VOCs): dichloromethane and trichloroethylene. Grafting of the vtmos and development of a “coating” of polysiloxane onto the adsorbent induced a modification of the carbon surface but also a partial filling of the porosity. These modifications accounted for a decrease of both the amounts of water and VOC adsorbed by the hydrophobised materials. However, water uptakes were found to be much lower than those of the VOCs, evidencing an enhanced selectivity of the hydrophobised adsorbents toward VOCs.     

Observing the Effects of Temperature and Surface Roughness on Cetyltrimethylammonium Bromide Adsorption Using a Quartz-Crystal Microbalance with Dissipation Monitoring

The effects of temperature and surface roughness on the mass and viscoelasticity of an adsorbed surfactant layer were monitored using a quartz crystal microbalance with dissipation monitoring (QCM-D). Adsorption isotherms at 30, 40, 50, and 60 °C and at two different roughnesses on gold were measured for cetyltrimethylammonium bromide (CTAB). All isotherms displayed an increase in mass and dissipation as surfactant concentration was increased to its critical micelle concentration (CMC). Above the CMC, adsorption reached a peak followed by a slight decrease to a plateau at the equilibrium adsorption value. As the temperature was increased, the adsorbed mass above the CMC decreased. The adsorbed mass decreased further by increasing substrate roughness, while the dissipation remained unchanged within experimental uncertainty. Dynamic adsorption experiments were also conducted at various temperatures for select concentrations above and below the CMC, providing evidence for the importance of different adsorption mechanisms as a function of both surfactant concentration and surface roughness.