Tensile properties of ultrathin double-walled carbon nanotube membranes

Direct tensile tests of double walled carbon nanotube (DWCNT) membranes with thickness of 40–80 nm were performed using a micro-stress-strain puller. The tensile strength and Young’s modulus are 4.8E2–8.4E2 MPa and 4.4–8.8 GPa, respectively. The deformation and fracture processes were analyzed using the stress vs. strain curves, and SEM observations of the fracture surface of a membrane. The membrane experienced elastic strain and plastic strain during tensile-loading to fracture, and the plastic process is due to the real plastic deformation of the membrane and the slippage between the DWCNT bundles. Cracks occur and spread during the tensile test which causes the membrane to be mangled. With these excellent mechanical properties, the DWCNT membranes can be used in nanotube-reinforced composites.     

Modification of Thin Film Composite PVA/PAN Membranes for Pervaporation Using Aluminosilicate Nanoparticles

The effect of the modification of the polyvinyl alcohol (PVA) selective layer of thin film composite (TFC) membranes by aluminosilicate (Al₂O₃·SiO₂) nanoparticles on the structure and pervaporation performance was studied. For the first time, PVA-Al₂O₃·SiO₂/polyacrylonitrile (PAN) thin film nanocomposite (TFN) membranes for pervaporation separation of ethanol/water mixture were developed via the formation of the selective layer in dynamic mode. Selective layers of PVA/PAN and PVA-Al₂O₃·SiO₂/PAN membranes were formed via filtration of PVA aqueous solutions or PVA-Al₂O₃·SiO₂ aqueous dispersions through the ultrafiltration PAN membrane for 10 min at 0.3 MPa in dead-end mode. Average particle size and zeta potential of aluminosilicate nanoparticles in PVA aqueous solution were analyzed using the dynamic light scattering technique. Structure and surface properties of membranes were studied using scanning electron microscopy (SEM), atomic force microscopy (AFM) and water contact angle measurements. Membrane performance was investigated in pervaporation dehydration of ethanol/water mixtures in the broad concentration range. It was found that flux of TFN membranes decreased with addition of Al₂O₃·SiO₂ nanoparticles into the selective layer due to the increase in selective layer thickness. However, ethanol/water separation factor of TFN membranes was found to be significantly higher compared to the reference TFC membrane in the whole range of studied ethanol/water feed mixtures with different concentrations, which is attributed to the increase in membrane hydrophilicity. It was found that developed PVA-Al₂O₃·SiO₂/PAN TFN membranes were more stable in the dehydration of ethanol in the whole range of investigated concentrations as well as at different temperatures of the feed mixtures (25 °C, 35 °C, 50 °C) compared to the reference membrane which is due to the additional cross-linking of the selective layer by formation hydrogen and donor-acceptor bonds between aluminosilicate nanoparticles and PVA macromolecules.     

Nano SiO2 and MgO Improve the Properties of Porous β-TCP Scaffolds via Advanced Manufacturing Technology

Nano SiO₂ and MgO particles were incorporated into β-tricalcium phosphate (β-TCP) scaffolds to improve the mechanical and biological properties. The porous cylindrical β-TCP scaffolds doped with 0.5 wt % SiO₂, 1.0 wt % MgO, 0.5 wt % SiO₂ + 1.0 wt % MgO were fabricated via selective laser sintering respectively and undoped β-TCP scaffold was also prepared as control. The phase composition and mechanical strength of the scaffolds were evaluated. X-ray diffraction analysis indicated that the phase transformation from β-TCP to α-TCP was inhibited after the addition of MgO. The compressive strength of scaffold was improved from 3.12 ± 0.36 MPa (β-TCP) to 5.74 ± 0.62 MPa (β-TCP/SiO₂), 9.02 ± 0.55 MPa (β-TCP/MgO) and 10.43 ± 0.28 MPa (β-TCP/SiO₂/MgO), respectively. The weight loss and apatite-forming ability of the scaffolds were evaluated by soaking them in simulated body fluid. The results demonstrated that both SiO₂ and MgO dopings slowed down the degradation rate and improved the bioactivity of β-TCP scaffolds. In vitro cell culture studies indicated that SiO₂ and MgO dopings facilitated cell attachment and proliferation. Combined addition of SiO₂ and MgO were found optimal in enhancing both the mechanical and biological properties of β-TCP scaffold.     

Organic-inorganic composite membranes as addition of SiO2 for high temperature-operation in polymer electrolyte membrane fuel cells (PEMFCs)

Organic-inorganic composite membranes for operation above 100 °C in polymer electrolyte membrane fuel cells (PEMFCs) were prepared, characterized and cell-tested. Composite membranes were obtained by mixing organic polymers, which have a SO₃H group as a proton conductor with inorganic material, SiO₂, using the sol-gel process. Electron probe micro analyser (EPMA) was used to show the homogeneous and uniform distribution of SiO₂. The physico-chemical properties of all membranes were investigated regarding their tensile strength, water uptake and thermogravimetric analyzer (TGA). Due to a higher water uptake and thermal stability of composite membranes, the cell performances at high temperatures above 100 °C, were improved. In addition, the SiOH group in the composite membrane was shown to play a major role in capturing water strongly and maintaining proton conductivity even at high temperature. Furthermore, the fuel cell performance of organic-inorganic composite membranes was superior to that of the Nafion membrane at high current density over all ranges of temperature.     

Preparation and Characterization of Plasma-Derived Fibrin Hydrogels Modified by Alginate di-Aldehyde

Fibrin hydrogels are one of the most popular scaffolds used in tissue engineering due to their excellent biological properties. Special attention should be paid to the use of human plasma-derived fibrin hydrogels as a 3D scaffold in the production of autologous skin grafts, skeletal muscle regeneration and bone tissue repair. However, mechanical weakness and rapid degradation, which causes plasma-derived fibrin matrices to shrink significantly, prompted us to improve their stability. In our study, plasma-derived fibrin was chemically bonded to oxidized alginate (alginate di-aldehyde, ADA) at 10%, 20%, 50% and 80% oxidation, by Schiff base formation, to produce natural hydrogels for tissue engineering applications. First, gelling time studies showed that the degree of ADA oxidation inhibits fibrin polymerization, which we associate with fiber increment and decreased fiber density; moreover, the storage modulus increased when increasing the final volume of CaCl₂ (1% w/v) from 80 µL to 200 µL per milliliter of hydrogel. The contraction was similar in matrices with and without human primary fibroblasts (hFBs). In addition, proliferation studies with encapsulated hFBs showed an increment in cell viability in hydrogels with ADA at 10% oxidation at days 1 and 3 with 80 µL of CaCl₂; by increasing this compound (CaCl₂), the proliferation does not significantly increase until day 7. In the presence of 10% alginate oxidation, the proliferation results are similar to the control, in contrast to the sample with 20% oxidation whose proliferation decreases. Finally, the viability studies showed that the hFB morphology was maintained regardless of the degree of oxidation used; however, the quantity of CaCl₂ influences the spread of the hFBs.     

Optimization of preparation conditions of poly(vinylidene fluoride)/graphene oxide microfiltration membranes by the Taguchi experimental design

Poly(vinylidene fluoride) (PVDF)/graphene oxide (GO) microfiltration membranes were prepared via phase inversion process. The Taguchi experiments were designed to optimize the preparation conditions of composite membranes. PVDF content, solution type, GO content, and poly-(N-vinyl-2-pyrrolidone) (PVP) content were chosen as important effecting parameters. Membrane filtration resistance was optimized by calculating the signal-to-noise (S/N) ratio of the parameters. The group of PVDF = 12 wt.%, solution type = N, N-dimethylacetamide (DMAC), GO = 3 wt.%, and PVP = 5 wt.% was the optimal combination, and solution type was the most effective factor. Scanning electron microscope (SEM) images showed that all membranes had thicker finger-like substructures. To further investigate the influence of GO on antifouling and mechanical properties, the pure PVDF and PVDF/GO composite membranes (3.0 wt.%) were prepared according to the optimum conditions. The PVDF/GO composite membranes presented better antifouling performances due to the improvement of membrane hydrophilicity. The tensile strength and Young's modulus reached values of 10.33 and 148.47 MPa, which corresponded to a 55.11% and 67.14% increase, respectively.     

Influence of lengths of millimeter-scale single-walled carbon nanotube on electrical and mechanical properties of buckypaper

The electrical conductivity and mechanical strength of carbon nanotube (CNT) buckypaper comprised of millimeter-scale long single-walled CNT (SWCNT) was markedly improved by the use of longer SWCNTs. A series of buckypapers, fabricated from SWCNT forests of varying heights (350, 700, 1,500 μm), showed that both the electrical conductivity (19 to 45 S/cm) and tensile strength (27 to 52 MPa) doubled. These improvements were due to improved transfer of electron and load through a reduced number of junctions for longer SWCNTs. Interestingly, no effects of forest height on the thermal diffusivity of SWCNT buckypapers were observed. Further, these findings provide evidence that the actual SWCNT length in forests is similar to the height.     

Synthesis and properties of soluble fluorinated poly(ether imide)s with different pendant groups

Two types of new fluorinated diamine monomer, [1,4-(4-amino-2-trifluoromethyl-phenoxy)-2-(3′-trifluoromethylphenyl) benzene (III)] and [1,4-(4-amino-2-trifluoromethyl-phenoxy)-2-(3′-methylphenyl) benzene (IV)] were synthesized and polymerized with aromatic dianhydrides. A series of soluble poly(ether imide)s (PEIs) were prepared from the diamines and dianhydrides by two-step chemical imidization methods. Experimental results indicated that all the PEIs had glass transition temperature between 230 °C and 247 °C, the temperature at 5% weight loss between 527 °C and 598 °C under nitrogen. The membranes hand tensile strengths in the range of 74-101 MPa, tensile modulus in the range of 1.9-2.6 GPa, and elongation at break from 20 to 28%. The cast membranes also exhibited high optical transparency, with a UV-vis absorption edge of 354-406 nm. Moreover, these PEIs membranes possessed low dielectric constants of 2.63-3.20 (at 1 MHz) and low water uptakes (<0.75 wt%).     

Primary study of novel poly(acrylic sodium)/poly(ether sulfone) composite ultrafiltration membranes (I) the preparation of composite membrane

The poly(acrylic sodium) (PAS)/poly(ether sulfone) (PES) composite ultrafiltration membranes were prepared by coating PAS membrane solution on PES support membrane. The effects of substrate membrane, the composition of PAS solution such as PAS concentration, the choice of the solvent and the additive, and the thickness of PAS active layer on the performance of the composite membranes were extensively investigated. The experimental results have indicated the optimal PAS/PES composite membranes, containing a PES substrate with MWCO of 70,000, together with a PAS top layer having a thickness of about 20 μm, were tested at room temperature and under the pressure of 0.6 MPa with the mass concentration of 0.005 g/L poly(ethylene glycol) (PEG) (Mw = 1000 g/mol) solution, a flux of 32.6 L/(m² h) and a rejection of 92.2% were obtained, which are superior to those of the common commercial membranes reported.     

Studies on the synthesis of sodium ates (NaH2PO4, Na2HPO4, Na3PO4) using membrane electrolysis

Comparative studies have been carried out on the electrosynthesis of sodium phosphates in the cathode compartment of an industrial membrane cell supplied with phosphoric acid of concentrations ranging from 1 to 2 mol dm^–3. The anode compartment of the cell was supplied with brine containing 25% NaCl. Du Pont Nafion^® membranes of types N-423, N-901 and N-961 were used. It was found that current efficiencies for the production of sodium phosphates exceeded 96%, this being higher than that for sodium hydroxide and, in spite of the different properties of the membranes, these efficiencies were similar. With N-423 membrane, the current efficiency was 2 3% lower than that for other membranes, but at the same time, the voltage of the cell was lower by 8 12%. Thus, N-423 membrane gives better performance during sodium phosphate synthesis as compared to membranes N-901 and N-961.     

A Competition between Hydrogen,Stacking, and Halogen Bonding in N-(4-((3-Methyl-1,4-dioxo-1,4-dihydronaphthalen-2-yl)selanyl)phenyl)acetamide: Structure,Hirshfeld Surface Analysis, 3D Energy Framework Approach,and DFT Calculation

N-(4-((3-Methyl-1,4-dioxo-1,4-dihydronaphthalen-2-yl)selanyl)phenyl)acetamide (5), C₁₉H₁₅NO₃Se, was prepared in two steps from 4,4′-diselanediyldianiline (3) via reduction and subsequent nucleophilic reaction with 2-methyl-3-bromo-1,4-naphthalenedione, followed by acetylation with acetic anhydride. The cytotoxicity was estimated against 158N and 158JP oligodendrocytes and the redox profile was also evaluated using different in vitro assays. The technique of single-crystal X-ray diffraction is used to confirm the structure of compound 5. The enantiopure 5 crystallizes in space group P21 with Flack parameter 0.017 (8), exhibiting a chiral layered absolute structure. Molecular structural studies showed that the crystal structure is foremost stabilized by N-H···O and relatively weak C-H···O contacts between molecules, and additionally stabilized by weak C-H···π and Se···N interactions. Hirshfeld surface analysis is used to quantitatively investigate the noncovalent interactions that stabilize crystal packing. Framework energy diagrams were used to graphically represent the stabilizing interaction energies for crystal packing. The analysis of the energy framework shows that the interactions energies of and C-H···π and C-O···π are primarily dispersive and are the crystal’s main important forces. Density functional theory (DFT) calculations were used to determine the compound’s stability, chemical reactivity, and other parameters by determining the HOMO-LUMO energy differences. The determination of its optimized surface of the molecular electrostatic potential (MEP) was also carried out. This study was conducted to demonstrate both the electron-rich and electron-poor sites.     

Preparation of a Facilitated Transport Membrane Composed of Carboxymethyl Chitosan and Polyethylenimine for CO2/N2 Separation

The miscibility of carboxymethyl chitosan/polyethylenimine (CMCS/PEI) blends was analyzed by FT-IR, TGA and SEM. Defect-free CMCS/PEI blend membranes were prepared with polysulfone (PSf) ultrafiltration membranes as support layer for the separation of CO₂/N₂ mixtures. The results demonstrate that the CMCS/PEI blend is miscible, due to the hydrogen bonding interaction between the two targeted polymers. For the blended membrane without water, the permeability of CO₂ gas is 3.6 × 10⁻⁷ cm³ cm⁻² s⁻¹ cmHg⁻¹ and the corresponding separation factor for CO₂ and N₂ gas is about 33 at the pressure of 15.2 cmHg. Meanwhile, the blended membrane with water has the better permselectivity. The blended membrane containing water with PEI content of 30 wt% has the permeance of 6.3 × 10⁻⁴ cm³ cm⁻² s⁻¹ cmHg⁻¹ for CO₂ gas and a separation factor of 325 for CO₂/N₂ mixtures at the same feed pressure. This indicates that the CO₂ separation performance of the CMCS/PEI blend membrane is higher than that of other facilitated transport membranes reported for CO₂/N₂ mixture separation.     

Flexible and robust YAG-Al2O3 composite nanofibrous membranes enabled by a hybrid nanocrystalline-amorphous structure

A flexible and robust YAG-Al₂O₃ composite nanofibrous membrane was fabricated by a combination of sol-gel and electrospinning methods, then a sintering at 900 °C. The effects of Al₂O₃ on the microstructure and mechanical performance of YAG nanofibrous membranes were investigated. The YAG nanofibrous membrane is brittle but the composite membranes exhibit a brittle-to-flexible transformation as the Al₂O₃ content reaches 30 wt.%, which can be attributed to an optimized dense hybrid microstructure consisting of finer YAG grain size surrounded by amorphous Al₂O₃. The YAG-30 wt.% Al₂O₃ nanofibrous membrane sintered at 900 °C shows a tensile strength of 3.52±0.31 MPa, three times of that of pure Al₂O₃ sintered at the same temperature. The membrane still presents a decent flexibility with a tensile strength of 0.75±0.25 MPa after sintering at 1000 °C, which is at least 100 °C higher than the sintering temperature of most reported ceramic nanofibrous membranes.     

The obtaining of high-density specimens and analysis of mechanical strength characteristics of a composite based on ZrO2-WC nanopowders

The structures, processes of shrinkage, and phase composition of the compact system ZrO₂-WC, obtained by hot pressing with the transmission of high current, are considered in the article. We found that as a result of compaction, the ZrO₂-WC-ceramics have uniform density distribution, with the following optimal mode consolidation values T = 1,350°C, P = 30 MPa and t = 2 min. These conditions allow us to achieve the best combination of ceramic properties by criteria density and strength.     

Effect of rhBMP-2 Immobilized Anorganic Bovine Bone Matrix on Bone Regeneration

Anorganic bovine bone matrix (Bio-Oss^®) has been used for a long time for bone graft regeneration, but has poor osteoinductive capability. The use of recombinant human bone morphogenetic protein-2 (rhBMP-2) has been suggested to overcome this limitation of Bio-Oss^®. In the present study, heparin-mediated rhBMP-2 was combined with Bio-Oss^® in animal experiments to investigate bone formation performance; heparin was used to control rhBMP-2 release. Two calvarial defects (8 mm diameter) were formed in a white rabbit model and then implanted or not (controls) with Bio-Oss^® or BMP-2/Bio-Oss^®. The Bio-Oss^® and BMP-2/Bio-Oss^® groups had significantly greater new bone areas (expressed as percentages of augmented areas) than the non-implanted controls at four and eight weeks after surgery, and the BMP-2/Bio-Oss^® group (16.50 ± 2.87 (n = 6)) had significantly greater new bone areas than the Bio-Oss^® group (9.43 ± 3.73 (n = 6)) at four weeks. These findings suggest that rhBMP-2 treated heparinized Bio-Oss^® markedly enhances bone regeneration.     

Enhanced BMP-2-Mediated Bone Repair Using an Anisotropic Silk Fibroin Scaffold Coated with Bone-like Apatite

The repair of large bone defects remains challenging and often requires graft material due to limited availability of autologous bone. In clinical settings, collagen sponges loaded with excessive amounts of bone morphogenetic protein 2 (rhBMP-2) are occasionally used for the treatment of bone non-unions, increasing the risk of adverse events. Therefore, strategies to reduce rhBMP-2 dosage are desirable. Silk scaffolds show great promise due to their favorable biocompatibility and their utility for various biofabrication methods. For this study, we generated silk scaffolds with axially aligned pores, which were subsequently treated with 10× simulated body fluid (SBF) to generate an apatitic calcium phosphate coating. Using a rat femoral critical sized defect model (CSD) we evaluated if the resulting scaffold allows the reduction of BMP-2 dosage to promote efficient bone repair by providing appropriate guidance cues. Highly porous, anisotropic silk scaffolds were produced, demonstrating good cytocompatibility in vitro and treatment with 10× SBF resulted in efficient surface coating. In vivo, the coated silk scaffolds loaded with a low dose of rhBMP-2 demonstrated significantly improved bone regeneration when compared to the unmineralized scaffold. Overall, our findings show that this simple and cost-efficient technique yields scaffolds that enhance rhBMP-2 mediated bone healing.     

High dielectric constant polyaniline/sulfonated poly(aryl ether ketone) composite membranes with good thermal and mechanical properties

All‐organic polyaniline (PANI)/sulfonated poly(aryl ether ketone) (SPAEK) composite membranes consisting of a PANI (conducting) filler evenly distributed in an SPAEK (insulating) matrix were prepared with a solution‐blending technique. The dielectric properties, electrical conductivity, and thermal and mechanical performances of the all‐organic PANI/SPAEK composite membranes were investigated as a function of different PANI loading levels. The composite membrane containing 30 wt % PANI exhibited a high dielectric constant of about 600, a low dielectric loss tangent of about 0.6 (at 1 kHz), and good thermal properties (temperature for 5% weight loss > 250°C) and mechanical properties (tensile strength ≈ 35 MPa). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1990–1995, 2013     

Semi-interpenetrating polymer networks of Nafion and fluorine-containing polyimide with crosslinkable vinyl group

Fluorine-containing polyimide with crosslinkable vinyl group (FPI) was synthesized from 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl (PFMB), and 4-amino styrene (AS). The reinforced composite membranes based on semi-interpenetrating polymer networks (semi-IPN) were prepared via solution casting of FPI and Nafion^®212, and crosslinking thereafter. The water uptake, swelling ratio, mechanical properties, thermal behavior, proton conductivity, and oxidative stability of the composite membranes were investigated. Compared with the recast Nafion^® 212, the composite membrane shows better mechanical properties and improved dimensional stability. The tensile strength of the composite membranes ranges from 39.0 MPa to 80.0 MPa, which is higher than that of the recast Nafion^® 212 membrane (26.6 MPa). The dimensional stability of the composite membranes increases with increasing FPI content in the membranes, whereas the proton conductivity decreases. The composite membranes show considerable proton conductivity from 2.0 × 10⁻² S cm⁻¹ to 8.9 × 10⁻² S cm⁻¹ at a temperature from 30 °C to 100 °C, depending on the FPI contents. The composite membranes with semi-IPN from FPI and Nafion^®212 have considerable high proton conductivity, excellent mechanical properties, thermal and dimensional stabilities.     

Development of CO2-Philic Blended Membranes Using PIM–PI and PIM–PEG/PPG

Blending is a simple method through which one can effectively tailor new polymers exhibiting the properties of their parent ones. Because the original properties of polymers are maintained after blending, various studies have used these films as gas separation membranes. In this study, a new CO₂ separation membrane is developed by physically mixing a polymer of intrinsic microporosity (PIM) with high gas permeability, polyimide (PIM-PI), as the hard segment and CO₂-philic PIM-poly(ethylene glycol)/poly(propylene glycol), or PIM-PEG/PPG, as the soft segment. Prepared by adding 5 mol.% of PIM-PEG/PPG to PIM-PI, the blended membrane PPB-5, with a tensile strength of 54 MPa and 35.5% elongation at break, shows better mechanical properties than commercial high-performance polymer membranes developed for gas separation, PEG-based blended membranes, and corresponding copolymer membranes with similar compositions developed in a previous study. In addition, it shows high CO₂ permeability (1552.6 Barrer) and CO₂/N₂ selectivity (29.3) due to the well-developed microphase separation characteristics originating from the optimal two-component composition, and the gas separation performance is close to the Robeson (2008) upper bound.