Characteristics and fluidic properties of porous monoliths prepared by radiation-induced polymerization for Lab-on-a-Chip applications

Porous polymer monoliths were prepared by UV- or EB-induced polymerization of hydroxyethyl methacrylate (HEMA) and ethylene dimethacrylate (EDMA) as network precursors dissolved in porogenic solvent mixtures composed of methanol and n-hexane. The fluidic properties and the pressure resistance of porous monoliths synthesized into 1 mm i.d. capillaries and in 100 μm-wide microchannels were investigated. The influence of photopolymerization time (or electron beam dose) and monomer content on flow properties is discussed on the basis of morphological features. The two types of radiation can be used to achieve the in situ fabrication of monolith inside microsystems. The permeability of the porous monoliths can be adjusted by tuning compositional and processing parameters.     

High-pressure phase behaviour measurement of (CO2 + ethylene glycol dimethacrylate) and (CO2 + di-ethylene glycol dimethacrylate) binary mixture systems

Ethylene glycol dimethacrylate (EGDMA) and di-ethylene glycol dimethacrylate (DEGDMA) are two of the most wildly used di-functional monomers in the polymer industry. The EGDMA and DEGDMA are applied to cross-linking polymerisation for improving the physical and chemical properties of synthesized polymers. However, residual and unreacted EGDMA and DEGDMA applied to the synthesis of dental composite and super-absorption polymer poses a health threat. This problem can be solved by using supercritical CO₂, which has high diffusivity and causes polymer swelling. To design and operate the supercritical fluid extraction process using scCO₂, high pressure phase behaviour data are required. The pressure–composition (P–x) isotherms for the (CO₂ + EGDMA) and (CO₂ + DEGDMA) binary mixture systems were measured using the static method with a variable-volume view cell at temperatures ranging from (313.2 to 363.2) K. The experimental data correlation was performed using the Peng–Robinson equation of state (PR-EOS) and the Van der Waals one fluid mixing rule. The critical constants for the PR-EOS were estimated by the Joback method and the Marrero–Gani method. The acentric factor was estimated by the Lee–Kesler method. The Marrero–Gani method showed better correlation results than the Joback method and the EGDMA is more soluble in the supercritical carbon dioxide than the DEGDMA.     

Macro- and microporous carbon monoliths with high surface areas pyrolyzed from poly(divinylbenzene) networks

Carbon monoliths with well-defined macropores and high surface areas were prepared by carbonization of macroporous poly(divinylbenzene) (PDVB) monoliths. The carbonization reactions of PDVB networks are studied by thermal analysis and FT-IR measurements. According to the measurement results, the PDVB networks are mostly pyrolyzed at 430 °C and their structures dynamically change to graphite-like structure between 600 and 700 °C. The macropore structure retained while the mesopores disappeared after carbonization. In addition, the surface area of the obtained carbons dramatically increased over 900 °C. The typical carbon monolith carbonized at 1000 °C for 2 h had a surface area of 1500 m² g^?1 and uniform macropores with a diameter of 1 μm.     

Anhydrous solid proton conductors based on perfluorosulfonic ionomer with polymeric solvent for polymer electrolyte fuel cell

Novel anhydrous polymeric proton conductors have been prepared from perfluorosulfonic acid ionomer with polymer solvent as supplying proton pathway through the segmental motion of polymer chains for polymer electrolyte fuel cell (PEFC) application. Since the membranes do not contain liquid-state acid or solvent, the membranes may promise more stable performances during the operation of PEFC. The Nafion-based anhydrous proton conductors showed maximum proton conductivity of about 4.0 × 10^?3 S cm^?1 at 130 °C under anhydrous condition. The mechanical properties of the membranes were enhanced by introducing H⁺-doped TiO₂ nanoparticles without the conductivity degradation. In addition, the electrochemical properties of the membrane electrode assembly (MEA) employing the anhydrous membrane as ionomer have been investigated, showing stable open circuit voltages (OCVs) over 0.9 V under non-humidified condition.     

Preparation of a poly(methyl methacrylate)-reduced graphene oxide composite with enhanced properties by a solution blending method

Poly(methyl methacrylate) (PMMA)/graphene nanocomposites were prepared by a simple solution blending method. The glass transition temperature of the produced PMMA/graphene composite was increased by 37 °C with 1.0 wt.% RGO content, which is approximately 40% of improvement compared to that of pure PMMA. The thermal expansion coefficient (TEC) decreased by 68% with as low as 0.1 wt.% RGO loading. The electrical conductivity of the nanocomposites reached up to 0.037 S/m even with only 2.0 wt.% RGO, which increased by more than twelve orders of magnitude. The resulting nanocomposites showed that a stable colloidal suspension of graphene dispersion in organic solvent before blending with PMMA is necessary to fabricate the nanocomposites with enhanced properties.     

Swelling characteristics and application of gamma-radiation on irradiated SBR-carboxymethylcellulose (CMC) blends

Blends of styrene butadiene rubber (SBR) with varying loading degree from 60 wt% to 100 wt% of carboxymethylcellulose (CMC) have been prepared. Gamma radiation vulcanization of prepared blends was carried out with doses varying between 50 kGy and 250 kGy. Mechanical properties, namely, tensile strength (Ts), elongation at break (E_b) and hardness were followed up as a function of loading degree of CMC and gamma irradiation dose. Moreover, physical properties, specifically swelling number (SN) and gel fraction % (GF%) were undertaken. Results obtained showed an improvement in mechanical as well as in physical properties with increasing either CMC content or dose of irradiation. Thermal properties namely thermo gravimetric analysis (TGA) was carried out.     

Extraction of Hemicelluloses from Corn Pericarp by the NaOH-Urea Solvent System

The NaOH-urea solvent system was applied for solubilization of hemicelluloses in corn pericarp (CP), an industrial waste of corn starch production, and the mechanical properties of films prepared from the isolated hemicelluloses were analyzed. CP was soaked in 0-8 wt% NaOH solutions containing 0-8 M urea, and the mixtures were frozen at -20 °C and thawed. By a simple recovery of the thawed solutions by filtration hemicelluloses were found to be solubilized efficiently above 2 wt% NaOH. The results of sugar compositional analysis indicate that the extracted materials were mixtures of hemicelluloses composed of arabinoxylan and β-(1,3;1,4)-glucan having arabinose/xylose ratios of 0.84-0.72. The present results indicated that NaOH solutions containing urea, with concentrations not enough to solubilize cellulose were adequate for extraction of hemicelluloses in CP. The hemicellulose extracted with 2 wt% NaOH-6 M urea could form transparent films whose mechanical properties were 56.2 MPa, 3.5% and 3.09 GPa for breaking stress (σmax), maximum strain (ɛmax) and elastic modulus (E), respectively, as evaluated by tensile tests. These values were 1.2-, 1.3- and 0.94-fold higher than those obtained by the film of arabinoxylan alone. Results suggest that β-glucan gives mechanical strength and flexibility to the stiff arabinoxylan films.     

Electron beam crosslinked gels—Preparation,characterization and their effect on the mechanical,dynamic mechanical and rheological properties of rubbers

Electron beam (EB) crosslinked natural rubber (NR) gels were prepared by curing NR latex with EB irradiation over a range of doses from 2.5 to 20 kGy using butyl acrylate as sensitizer. The NR gels were systematically characterized by solvent swelling, dynamic light scattering, mechanical and dynamic mechanical properties. These gels were introduced in virgin NR and styrene butadiene rubber (SBR) matrices at 2, 4, 8 and 16 phr concentration. Addition of the gels improved the mechanical and dynamic mechanical properties of NR and SBR considerably. For example, 16 phr of 20 kGy EB-irradiated gel-filled NR showed a tensile strength of 3.53 MPa compared to 1.85 MPa of virgin NR. Introduction of gels in NR shifted the glass transition temperature to a higher temperature. A similar effect was observed in the case of NR gel-filled SBR systems. Morphology of the gel-filled systems was studied with atomic force microscopy. The NR gels also improved the processability of the virgin rubbers greatly. Both the shear viscosity and the die swell values of EB-irradiated gel-filled NR and SBR were lower than their virgin counterparts as investigated by capillary rheometer.     

Graphene prepared by one-pot solvent exfoliation as a highly sensitive platform for electrochemical sensing

Graphene was easily obtained via one-step ultrasonic exfoliation of graphite powder in N-methyl-2-pyrrolidone. Scanning electron microscopy, transmission electron microscopy, Raman and particle size measurements indicated that the exfoliation efficiency and the amount of produced graphene increased with ultrasonic time. The electrochemical properties and analytical applications of the resulting graphene were systematically studied. Compared with the predominantly-used reduced graphene oxides, the obtained graphene by one-step solvent exfoliation greatly enhanced the oxidation signals of various analytes, such as ascorbic acid (AA), dopamine (DA), uric acid (UA), xanthine (XA), hypoxanthine (HXA), bisphenol A (BPA), ponceau 4R, and sunset yellow. The detection limits of AA, DA, UA, XA, HXA, BPA, ponceau 4R, and sunset yellow were evaluated to be 0.8 μM, 7.5 nM, 2.5 nM, 4 nM, 10 nM, 20 nM, 2 nM, and 1 nM, which are much lower than the reported values. Thus, the prepared graphene via solvent exfoliation strategy displays strong signal amplification ability and holds great promise in constructing a universal and sensitive electrochemical sensing platform.     

Highly porous electrodes from novel corn grains-based activated carbons for electrical double layer capacitors

In this study, novel corn grains-based activated carbons (CG-ACs) were prepared and their use as electrodes in the electrical double layer capacitor (EDLC) performed successfully. The structural properties, energetic heterogeneities and surface functional groups of CG-ACs were characterized using different techniques like nitrogen sorption data, adsorption energy distribution (AED) and X-ray photoelectric spectroscopy (XPS). The electrochemical properties of various CG-ACs were evaluated by using cyclic voltammetry. The maximum specific capacitance value as 257 F g⁻¹ was obtained in 6 M KOH electrolyte solution. The effects of various properties of the porous carbon materials on the EDLC performance were discussed.     

Morphological and thermal behavior of porous biopolymeric nanoparticles

The aim of the present work is to design, develop and characterize biodegradable polymeric nanoparticles having well defined size and porous morphology. Poly(dl-lactide-co-glycolide) (PLGA) and poly(l-lactide) (PLLA) nanoparticles (NPs) were prepared by double emulsion method with subsequent solvent evaporation. NPs were characterized by electron microscopes, dynamic light scattering, XRD and thermal properties by differential scanning calorimetry and thermogravimetry. Finally, the in vitro degradation analysis was also performed. Biodegradable NPs display a spherical surface structure with a homogeneous size distribution, and an average diameter of 180 nm for PLLA and 218 nm for the PLGA. The NP nanoporous structure was analyzed by an innovative thermal method: thermoporosimetry, providing information about nanopore dimensions. In vitro degradation studies demonstrate the gradual surface aggregation and degradation of NPs and the effects on polymer properties. Biopolymeric porous nano-systems may offer promise properties for revolutionary improvements in tissue engineering, diagnosis and targeted drug delivery systems.     

Thermodynamic models for determination of the solubility of dibenzothiophene in (methanol + acetonitrile) binary solvent mixtures

In this paper, we focused on solubility and solution thermodynamics of dibenzothiophene. By the gravimetric method, the solubility of dibenzothiophene was measured in (methanol + acetonitrile) binary solvent mixtures at temperatures from (278.15 to 333.15) K under atmosphere pressure. The solubility data were fitted using a modified Apelblat equation, a variant of the combined nearly ideal binary solvent/Redich–Kister (CNIBS/R–K) model and Jouyban–Acree model. Computational results showed that the modified Apelblat equation was superior to the other two equations. In addition, the thermodynamic properties of the solution process, including the Gibbs free energy, enthalpy, and entropy, were calculated by the van’t Hoff analysis. The experimental results showed that methanol could be used as effective anti-solvents in the crystallization process.     

Controllabe growth of cadmium hydroxide nanostructures by hydrothermal method

We proposed a general hydrothermal strategy for the fabrication of one-dimensional cadmium hydroxide nanostructures.Through controlled experimental conditions, such as solvent properties, salt concentration and alkaline concentration, the different morphologies and dimensions of the final products have been controlled. With this method, Cd(OH)₂ nanowires were prepared readily. XRD, TEM, FESEM and UV-vis absorption spectroscopy were used to characterize the nanowires product, which revealed that the Cd(OH)₂ nanowires consisted of about 30 nm in diameter and length up to several hundreds of nanometers. The optical absorption spectrum indicates that the Cd(OH)₂ nanowires have a indirect band gap of ～2.56 eV. In addition, the as-prepared Cd(OH)₂ nanowires acting as a precursor was converted into porous cadmium oxide through dehydration.     

Morphosynthesis of poly(ether ketone) by reaction-induced crystallization during polymerization

Morphology control of poly(ether ketone) (PEK) was examined by using the crystallization during the nucleophilic aromatic substitution reaction of potassium salt of 4-fluoro-4′-hydroxybenzophenone. Polymerizations were carried out at 290 °C. The PEK was obtained as precipitates and its morphology was highly influenced by the polymerization condition such as the solvent, the concentration and the polymerization time. High crystalline spindle-like crystals were obtained by the polymerization in diphenyl sulfone (DPS) at a concentration of 5.0% for 2 h with the yield of 86%. The average length and width were 1.4 μm and 300 nm respectively, and the maximum thickness was 130 nm. The surface was not smooth and it was hilly. The spindle-like crystal was likely consisted of multilayered lamellae comprised of the microcrystallites. The molecules were oriented perpendicular to the lamella. The polymerization in DPS at a higher concentration of 10.0% afforded the networks of nanofibres, of which the diameter was 100–250 nm. The obtained PEK precipitates possessed excellent thermal properties.     

Investigation of sodium 4-nitrotoluene-2-sulfonate solubility in aqueous organic solutions

The solubility of sodium 4-nitrotoluene-2-sulfonate (NTSNa) in binary solvent mixtures (methanol + water), (ethanol + water), and (2-methoxyethanol + water) was investigated over the temperature range from (288 to 344) K. The mole fraction of water in solvent mixtures ranged from 0 to 0.8. The solubility data are described by the electrolyte non-random two-liquid (E-NRTL) model. The E-NRTL binary interaction parameters are expressed as a function of temperature, and were obtained from the experimental data. The root-mean-square deviations of solubility temperature varied from (0.20 to 1.35) K.     

Effect of radiation dose on the properties of natural rubber nanocomposite

Effect of radiation dose and carbon nanotubes (CNT) on the mechanical properties of standard Malaysian rubber (SMR) was investigated in this study. SMR nanocomposites containing 1–7 phr CNT were prepared using the solvent casting method and the nanocomposites were radiated at doses of 50–200 kGy. The change in mechanical properties, especially, tensile strength (Ts), elongation at break (Eb), hardness and tensile modulus at 100% elongation (M₁₀₀) were studied as a function of radiation dose. The structure and morphology of reinforced natural rubber was investigated by FESEM, TEM and AFM in order to gain further evidence on the radiation-induced crosslinking. It was found that the Ts, M₁₀₀ and the hardness of the SMR/CNT nanocomposites significantly increased with radiation dose; the elongation at break exhibited an increase up to 100 kGy, and a downward trend thereafter. Results on gel fraction further confirmed the crosslinking of SMR/CNT nanocomposites upon radiation.     

Preparation of sulfonated poly(phthalazinone ether sulfone ketone) composite nanofiltration membrane

Thin film composite (TFC) membranes were prepared from sulfonated poly(phthalazinone ether sulfone ketone) (SPPESK) as a top layer coated onto poly(phthalazinone ether sulfone ketone) (PPESK) ultrafiltration (UF) support membranes. The effects of different preparation conditions such as the SPPESK concentration, organic additives, solvent, degree of substitution (DS) of SPPEK and curing treatment temperature and time on the membrane performance were studied. The SPPESK concentration in the coating solution was the dominant factor for the rejection and permeation flux. The TFC membranes prepared from glycerol as an organic additive show better performance then those prepared from other additives. The rejection increased and the flux decreased with increasing curing treatment temperatures. The salt rejections of the TFC nanofiltration (NF) membranes increased in the order MgCl₂ < MgSO₄ < NaCl < Na₂SO₄. TFC membranes showed high water flux at low pressure. SPPESK composite membranes rejections for a 1000 mg L⁻¹ Na₂SO₄ feed solution was 82%, and solution flux was 68 L m⁻² h⁻¹ at 0.25 MPa pressure.     

A BET model of the thermodynamics of aqueous multicomponent solutions at extreme concentration

The statistical mechanical basis of the use of Brunauer-Emmett-Teller isotherms to represent activities and other thermodynamic properties in extremely concentrated solutions was established by Ally and Braunstein (J. Chem. Thermodynamics1998, 30, 49–58) for a two-salt, single-solvent, mixture. Based upon the work of these authors, we have derived equations for solute and solvent activities in liquid mixtures containing a single solvent and indefinite number of solutes. New terms have been added to the model equations to express the effects of ternary ion interactions on the salt adsorption parameters. Solution composition is defined on the basis of salts, rather than ions, as components. As examples, the model is used to represent water activities in concentrated (lithium nitrate  +  potassium nitrate  +  water) and (lithium ion  +  sodium ion  +  chloride ion  +  nitrate ion  +  water) mixtures, and salt solubilities in (calcium chloride  +  calcium nitrate  +  water) mixtures.     

Preparation and properties of cellulose/PE-co-AA blends

Cellulose/polyethylene-co-acrylic acid blends (cellulose concentration 0–50 wt.%) was prepared via mixing their alkaline solutions. The formed suspension was precipitated and dried, where after the morphology as well the thermal and mechanical properties of the blends were characterized by Differential Scanning Calorimetry (DSC), Scanning Electron Microscopy (SEM), and Dynamic Mechanical Analyses (DMA). In addition, the melt properties of the blend were studied by rotational rheometer following some injection molding trials as well. The polymers were found to be dispersed homogenously in the blend and the crystallization temperature of the PE-co-AA phase was increased ～6 °C due to the nucleation ability of the cellulose phase. The size of the discontinuous cellulose phase was 5 μm at the most while at higher cellulose concentrations (30–50 wt.%) the polymers formed co-continuous morphology in the blend. This change in the morphology was observed also in their melt properties which showed that the blend reached so called percolation point at ～20 wt.% of cellulose. Finally, the blends were found to be injection moldable over the whole composition range, if only the injection molding became more challenging (i.e. higher mold temperatures and longer mold cooling times were required) after the percholation point.     

Application of Potassium Carbonate as Space Holder for Metal Injection Molding Process of Open Pore Copper Foam

Copper foam has recently being applied to replace aluminium as heat sink. In this study, copper foam was manufactured via metal injection molding technique. Copper feedstock were prepared comprising 0 wt.%, 30 wt.% and 40 wt.% of potassium carbonate into copper powder to produce open pore cell structure, which also mixed together with a binder system consisting palm stearin (PS), polyethylene (PE) and stearic acid (SA). The feedstock was then injection molded into tensile shape test piece prior to solvent extracted in heptane prior to sintering using tube furnace at 850^oC for 4 hours in nitrogen atmosphere. The sintered samples were immersed in warm water to dissolve the carbonates. Copper foam has successfully manufactured at 850^oC for 4 hours in nitrogen atmosphere followed by the dissolution process. The porosity value increased as the addition of potassium carbonate increased from 0 to 40 wt.% which given the highest value of 52.985% porosity and thermal conductivity of 520.46 W/m.K.