Antimicrobial polyurethane synthetic leather coating with In-situ generated Nano-TiO2

By incorporating organic-inorganic nano-hybridization into wet phase inversion coating-forming method, a novel antimicrobial polyurethane synthetic leather coating with in-situ generated nano-TiO₂ (PUT) was prepared. The antibacterial activity against Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Micrococcus luteus, antifungal activity against Aspergillus niger and toxicity of this PUT coating were investigated respectively. Experimental results showed that the antimicrobial activity of the PUT coating increased with increasing nano-TiO₂ concentration. Low nano-TiO₂ concentration (≤0.50 wt%) resulted in negligible or limited antimicrobial activity. When the nano-TiO₂ concentration increased up to 0.75 and 1.00 wt%, the antibacterial activity of the PUT coating exceeded 82 and 93 % respectively, and no Aspergillus niger growth was observed on the coating surface within 28 days. Cell culture assay indicated that the PUT coating had no detrimental effect on the morphologies and proliferation rate of normal human dermal fibroblasts, which indicated a non-toxic and skin-friendly characteristic. According to these results, the PUT coating was capable of reducing the risk of microbial contamination while remained skin-friendly to wearers. More importantly, the organic-inorganic nano-hybridization technique developed in this study was carried out simultaneously during the established wet phase inversion coating-forming method for PU leather manufacture, which promised its possible application on an industrial scale.     

Preparation of Polyurethane Silicon Oxide Nanomaterials as a Binder in Leather Finishing

Leather finishing processes using toxic organic solvent based produce volatile organic compounds (VOC), chronic exposure to this chemicals effect on workers' health causing many diseases especially lung cancer. So, polyurethane waterbased was synthesized for application in leather finishing instead of organic solvent based because it’s economic and safety for industry and workers. Preparation of water-based polyurethane (PU) depends on the reaction of polyethylene glycol (PEG, 300) with isophorone diisocyanate (IPDI) and the reaction of IPDI-1,4-butanediol (BDO) together with dimethylolpropionic acid (DMPA), was synthesized by poly-addition polymerization reaction. PU was then modified with different amounts of silicon dioxide nanoparticles (1-5 % SiO₂), used as a binder in leather finishing. Leather coated was characterized physically, chemically and thermally by FTIR, GPC, DLS, TEM, SEM and TGA. The results revel that, water vapor permeability (WVP) of leather coated with PU modified with SiO₂ showed improvement due to the existence of SiO₂ particles which increases the interspaces of the polyurethane coating. SEM showed that when the amount of SiO₂ nanoparticles increases, there is uniform nanoparticles accumulated can be observed. EDX prove the presence of Si and O₂ elements and the formation of SiO₂ nanoparticles. Mechanical properties discussed that tensile strength; tear strength and elongation at break % increase with increase SiO₂ concentration until 3 % SiO₂ nanoparticles. TGA showed an improvement of thermal stability of coated leather modified with SiO₂. Therefore, this study succeeded in preparation of safe, ecofriendly of water-based polyurethane binders which modified with SiO₂ for using in leather finishing.     

Electrospun in-situ hybrid polyurethane/nano-TiO<Subscript>2</Subscript> as wound dressings

By combining the organic-inorganic hybridization, wet phase inversion, and electrospinning, novel electrospun polyurethane (PU) membranes with in-situ generated nano-TiO₂ were prepared, which satisfied the requirements of an ideal wound dressing. The morphology of the PU-TiO₂ mats and the cross sectional morphologies of the membranes were characterized by a scanning electron microscopy (SEM). The average diameter of the individual fibers obtained from the solutions was 341±12 nm. SEM micrographs with higher magnification further showed that the in-situ generated TiO₂ particles were well-separated and dispersed homogeneously in the membranes. The average sizes of TiO₂ particles were increased from 31 to 57 nm, with the increase of nano-TiO₂ concentration. The water vapor transmission rates (WVTRs) of the membranes were in the range of 373.55–3121.86 g/m²·d and decreased gradually with the increase of nano-TiO₂ concentration. The water absorption of various PU membranes was in the range of 210.90–397.98 % which was enough to prevent wound beds from exudate accumulation. Shake flask testing indicated that the PU membrane exhibited antibacterial efficiency against Pseudomonas aeruginosa (Ps. aeruginosa) and Staphylococcus aureus (S. aureus) due to in-situ generated of nano-TiO₂. These electrospun nanofibrous membranes also had no toxic effect and showed good and immediate adherence to L929 cells.     

Crystallization of poly(vinylidene fluoride)-SiO2 hybrid composites prepared by a Sol-gel process

Organic-inorganic hybrid composites consisting of poly(vinylidene fluoride) (PVDF) and SiO₂ were prepared through a sol-gel process and the crystallization behavior of PVDF in the presence of SiO₂ networks was investigated by spectroscopic, thermal and x-ray diffraction measurements. The hybrid composites obtained were relatively transparent, and brittleness increased with increasing content of tetraethoxysilane (TEOS). It was regarded from FT-IR and DSC thermal analyses that at least a certain interaction existed between PVDF molecules and the SiO₂ networks. X-ray diffraction measurements showed that all of the hybrid samples had a crystal structure of PVDFγ-phase. Fresh gel prepared from the sol-gel reaction showed a very weak x-ray diffraction peak near 2θ=21° due to PVDF crystallization, and intensity increased gradually with time after gelation. The crystallization behavior of PVDF was strongly affected by the amount of SiO₂ networks. That is, SiO₂ content directly influenced preference and disturbance for crystallization. In polymer-rich hybrids, SiO₂ networks had a favorable effect on the extent of PVDF crystallization. In particular, the maximum percent crystallinity of PVDF occurred at the content of 3.7 wt% SiO₂ and was higher than that of pure PVDF. However, beyond about 10 wt% SiO₂, the crystallization of PVDF was strongly confined.     

Facile Fabrication of Electrospun Silica Nanofibrous Membrane with Hydrophobic,Oleophilic and Breathable Performances

We report a simple and versatile method to prepare hydrophobic composite SiO₂ membrane. The electrospun SiO₂ membrane was selected due to its good flexibility and thermal stability. The hydrophobic SiO₂ membrane was succussfully prepared by simply evaporating a thin polydimethylsiloxane (PDMS) layer on the fiber surface. The characterization results show that the PDMS layer is too thin to be observed. The PDMS coating has no influence on the porous structure of the fibrous membrane, but imparts the good hydrophobicity and oleophilicity to the SiO₂ nanofibers. As demonstration, the hydrophobic SiO₂-PDMS membrane displays good oil absorption performance from the oil/water mixture, as well as filtration membrane for oil/water separation. Additionally, due to the proper pore size and hydrophobic surface, the SiO₂- PDMS membrane shows good waterproof performance and breathability at the same time.     

Preparation and acid dye adsorption behavior of polyurethane/chitosan composite foams

We prepared a series of polyurethane(PU)/chitosan composite foams with different chitosan content of 5∼20 wt% and investigated their adsorption performance of acid dye (Acid Violet 48) in aqueous solutions with various dye concentrations and pH values. It was observed that PU/chitosan composite foams exhibited well-developed open cell structures. Dye adsorption capacities of the composite foams increased with the increment of chitosan content in composite foams, because amine groups of chitosan serve as the binding sites for sulfonic ions of acid dyes in aqueous solutions. In addition, dye adsorption capacities of composite foams were found to increase with decreasing the pH value, which stems from the fact that the enhanced chemisorption between protonated amine groups of chitosan and sulfonic ions of acid dye is available in acidic solutions. The dye adsoption kinetics and equilibrium isotherm of the composite foams were well described with the pseudo-second order kinetic model and Langmuir isotherm model, respectively. The maximum adsorption capacity (q _max) for the PU/chitosan composite foams with 20 wt% chitosan content is evaluated to be ca. 30 mg/g.     

Si-Al hybrid effect of waterborne polyurethane hybrid sizing agent for carbon fiber/PA6 composites

The interface of fiber-reinforced composites has remained a vexing problem that limits the use of the excellent properties of carbon fiber (CF) in composite applications. In the present study, waterborne polyurethane (WPU) hybrid sizing agents were prepared to improve the performances of CFs and the interface strength of CF/PA6 composites. The structural and mechanical properties of the single-CF and CF/PA6 composites were systematic investigated. The results showed that the mechanical properties of the CF/PA6 composites were significantly improved by adding of WPU hybrid sizing agent. The tensile and flexural strengths of the WPU/SiO₂/Al₂O₃ hybrid sizing agent treated CF/PA6 composites were increased by 24.0 % and 25.7 % than those of no-sizing treated CF/PA6 composites, respectively.     

Functionalization of lyocell fibers with TiO2, SiO2, and GLYMO

In the research self-cleaning coatings based on photocatalytically active nano titanium dioxide (TiO₂) were prepared. When applied directly to cellulose fiber surfaces, TiO₂ coatings form weak bonds with fibers. Therefore 3-glycidooxypropyl-trimethoxysilane was used as a coupling agent. It had been applied on the surface of cellulose fibers before the TiO₂ coating was performed. In this case, the silane is in the interface region, where it can be most effective as an adhesion promoter. Silane coupling agents have unique chemical and physical properties not only to enhance bond strength, but more importantly to prevent de-bonding at the interface during composite aging and use as well. The coupling agent provides a stable bond between two otherwise poorly bonding surfaces. Surface properties of these coatings have been examined, such as surface morphology and surface microstructure. TiO₂ nanoparticles were irreversibly attached to the surface of monodisperse silica (SiO₂) spheres and to the surface of Lyocell fibers coated with an epoxy-containing silane coupling agent. Analysis using scanning electron microscopy showed uniform distribution of nanoparticles in the resulting coatings. Fourier transform infrared spectroscopy revealed changes in the surface microstructure occurring after different modifications. In addition, the influence of photocatalytic activity on the mechanical properties of Lyocell fibers was determined. In addition to that, the results indicated that SiO₂ and the coupling agent provide a protection against high oxidizing power of TiO₂ under exposure to daylight irradiation.     

Preparation of collagen fiber/CaCO3 hybrid materials and their applications in synthetic paper

The collagen fiber/CaCO₃ hybrid materials were successfully prepared via in situ organic-inorganic hybrid technique. The surface morphology, hybrid mechanism, thermal and hydrothermal stability of these materials were investigated, respectively. Scanning electron microscopy (SEM) analysis showed that the size scale and distribution of CaCO₃ particles in collagen fiber relied on the concentration of CaCl₂. When the CaCl₂ was at low concentration, for example 6 wt%, the in-situ produced CaCO₃ particles were distributed evenly around the collagen fiber, the particle size could be controlled in the range of 2–4 µm and no apparent coagulation of CaCO₃ particles was found. Fourier transform infrared spectroscopy (FTIR) study revealed the interactions between the collagen fiber and CaCO₃ particles. The water solubility test and TGA analysis indicated that the solubility of collagen fiber in hot water decreased significantly after hybridization with CaCO₃ particles, whereas, the decomposition temperature was improved with increasing of the production of CaCO₃ particles. Moreover, the hybrid materials were used in conjunction with polyurethane and CaCO₃ powder to fabricate a novel synthetic paper. The result showed that the synthetic paper had good writing and printing.     

Performance of PTT fabric treated with CNTs/SiO<Subscript>2</Subscript>/thiazole dye hybrid materials

A series of CNTs/SiO₂/thiazole dye hybrid materials prepared via the sol-gel process is synthesized from carbon nanotubes (CNTs) and tetraethoxysilane with heteroaryl 4-phenyl-2-amino-thiazole dyes. Heterocyclic 4-phenyl-2-aminothiazole dyes are processed with the hydrolysis-condensation reaction at a constant ratio of vinyltriethoxysilane and tetraethoxysilane condensed with modified CNTs in appropriate proportion under a catalyst. The structures of the CNTs/SiO₂/thiazole dye hybrid materials are characterized by Fourier transform infrared spectroscopy (FTIR). Polytrimethylene terephthalate (PTT) fabrics are used to evaluate the morphology structure by scanning electron microscopy (SEM). SEM images show that a uniform dyeing on the PTT fabrics to confirm the reaction of hybrid materials with PTT fabrics. The washing fastness, color evenness, water contact angle, air permeability, electric conductivity, and weatherability of PTT fabrics dyed with CNTs/SiO₂/thiazole dye hybrid materials are evaluated, with results indicating improved conductivity and water-repellent.     

Polyaniline-doped TiO<Subscript>2</Subscript>/PLLA fibers with enhanced visible-light photocatalytic degradation performance

A simple and practical strategy has been developed for preparing polyaniline(PANi)-doped TiO₂/poly(l-lactide) (P@TiP-C) fibers by a combination of coaxial-electrospinning and in-situ polymerization. The TiO₂/PLLA composite fibers with TiO₂ located on the surface were fabricated by coaxial-electrospinning, with PLLA as the core phase and a dispersion of TiO₂ particles, a well-known photocatalyst, in the sheath phase. The aniline monomers were also located in the core phase and in-situ polymerized by ammonium persulfate (APS) after electrospinning. SEM images show that TiO₂ particles were located on the surface of PLLA fibers. Photocatalytic degradation tests show that the P@TiP-C fibers exhibit enhanced photocatalytic activity for degradation of methyl orange under visible light, likely due to the synergistic effect of PANi and TiO₂.     

The synergy effect of Graphene/SiO<Subscript>2</Subscript> hybrid materials on reinforcing and toughening epoxy resin

Based on the situ preparation of silica nanoparticles (SiO₂) on the surface of Graphene nanoplatelets (GNPs) in the previous work, these unique three dimensional (3D) materials were introduced into epoxy resin to study the reinforcing and toughening synergy effect on the composites. Firstly, the tensile tests showed that Graphene/SiO₂ hybrid materials attached with different size of SiO₂ particles exhibited different reinforcing and toughening effect on the composites. With the increasing of the diameter of SiO₂ particles, the toughness and strength properties of the composites firstly improved and then decreased, and when the average diameter was 0.14 μm, the elongation reached the max.. Meanwhile, the fractured surfaces presented on SEM images were consistent with the results of the tensile tests, which further explained the hybrid materials increased the interfacial adhesion between the fillers and matrix, leading to significant improvement in mechanical properties. Moreover, the DSC curves demonstrated that Graphene/SiO₂ hybrid materials accelerated the curing process of epoxy resin due to the cross-link structure between fillers and matrix. Lastly, the crack propagation modes were built to clarify the synergy effect mechanism of reinforcing and toughening on nanoparticles/epoxy resin composites.     

Low temperature shape recovery effect of polyurethane copolymer grafted with pendant <Emphasis Type="Italic">n</Emphasis>-butyl group

Effect of the pendant n-butyl group on shape recovery and tensile properties of polyurethane (PU) block copolymer was investigated. The grafted n-butyl group was intended to keep PU chains away and to deter molecular interaction between PU chains by its flexible chains, and thus improve shape recovery at subzero temperature while maintaining high and reproducible tensile properties and shape recovery at ambient temperature. The attachment of n-butyl group did not make any change in the molecular interaction and phase separation of hard and soft segments in PU structure as judged from IR and DSC analysis. Cross-link density and intrinsic viscosity increased with the increase of n-butyl content due to the partial cross-linking by the linking reagent. Shape recovery and shape retention were not diminished after cyclic shape memory tests. Finally, the effect of n-butyl group on low temperature shape recovery was compared with linear ones and the potential application of this finding was discussed.     

Microstructure and mechanical properties of polyurethane/nylon/montmorillonite nanocomposite

Nanocomposite of polyurethane (PU), Nylon66 (nylon), and montmorillonite (MMT) was prepared by a twin screw extruder, and the dispersion of MMT and the mechanical properties of the nanocomposite were analyzed. Dimethyl hydrogenated tallow 2-ethylhexyl ammonium modified Cloisite 25A (C25A) and methyl tallow bis-2-hydroxyethyl ammonium modified Cloisite 30B (C30B) were used as MMT. XRD and TEM analysis indicated that the continuous melt mixing by a twin screw extruder was effective in MMT dispersion. C30B having hydroxyl group on its surface has better dispersion than C25A in the PU/nylon matrix. Maximum stress and strain at break were the maximum at 1 wt% MMT regardless of matrix composition, and decreased at higher MMT content. Best MMT dispersion was also observed at 1 wt% MMT for the entire matrix composition. Aggregation of MMT occurred at MMT content higher than 1 wt%. Nylon addition also induced the aggregation of MMT because of the high polarity of nylon surface. Dispersion of MMT was very important in improving the mechanical properties of PU/nylon nanocomposite.     

Development of nanofibrous membranes with far-infrared radiation and their antimicrobial properties

This study investigated the incorporation of nanoscale germanium (Ge) and silicon dioxide (SiO₂) particles into poly(vinyl alcohol) (PVA) nanofibers with the aim of developing nanostructures with far-infrared radiation effects and antimicrobial properties for biomedical applications. Composite fibers containing Ge and SiO₂ were fabricated at various concentrations of Ge and/or SiO₂ using electrospinning and layered on polypropylene nonwoven. The morphological properties of the nanocomposite fibers were characterized using a field-emission scanning electron microscope and a transmission electron microscope. The far-infrared emissivity and emissive power of the nanocomposite fibers were examined in the wavelength range of 5-20 μm at 37 °C. The antibacterial properties were quantitatively assessed by measuring the bacterial reductions of Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli. Multi-component composite fibers electrospun from 11 wt% PVA solutions containing 0.5 wt% Ge and 1 wt% SiO₂ nanoparticles exhibited a far-infrared emissivity of 0.891 and an emissive power of 3.44·102 W m^?2 with a web area density of 5.55 g m^?2. The same system exhibited a 99.9 % bacterial reduction against both Staphylococcus aureus and Escherichia coli, and showed a 34.8 % reduction of Klebsiella pneumoniae. These results demonstrate that PVA nanofibrous membranes containing Ge and SiO₂ have potential in medical and healthcare applications such as wound healing dressings, skin care masks, and medical textile products.     

Electrical properties of graphene/waterborne polyurethane composite films

Graphene is classified as a carbon-based material. Structurally, graphene is made up of carbon-based two-dimensional atomic crystals and a one atom thick planar sheet of sp²-bonded carbon atoms. This sort of arrangement in graphene makes it a unique material with exceptional mechanical, physicochemical, thermal, electrical, optical, and biomedical properties. Methods for graphene-based fabric production mainly use graphene-based materials such as graphene (G), graphene oxide (GO), and reduced graphene oxide (rGO) coated on fabric or yarn. Waterborne polyurethane (WPU) is one of the most rapidly developing and active branches of polyurethane chemistry. More and more attention is being paid to graphene-coated fabrics owing to their low temperature flexibility, the presence of zero or very few VOCs (volatile organic compounds), water resistance, pH stability, superior solvent resistance, excellent weathering resistance, and desirable chemical and mechanical properties. It is used as a coating agent or adhesive for fibers, textiles, and leather. Also, graphene-containing materials have been used to enhance the properties of WPU. In this study, graphene/WPU composite solution and film was prepared to conduct basic research for developing electrical heating textiles which is not harmful to the human body, flexible and excellent in electrical properties. Graphene/WPU composite solutions were prepared with a graphene content of 0, 2, 4, 8, and 16 wt%, and graphene/WPU film was prepared with solution casting method. The graphene contents were analyzed for their surface morphology, electrical properties, and electrical heating properties.     

Electrospun SiO<Subscript>2</Subscript>/PMIA nanofiber membranes with higher ionic conductivity for high temperature resistance lithium-ion batteries

The nanofiber membrane prepared by electrospinning has been widely applied in lithium-ion batteries. A powerful strategy for designing, fabricating and evaluating Poly-m-phenylene isophthalamide (PMIA) nanofiber membrane with SiO₂ nanoparticles was developed by electrospinning in this paper. The morphology, crystallinity, thermal shrinkage, porosity and electrolyte uptake, and electrochemical performance of the SiO₂/PMIA nanofiber membranes were investigated. It was demonstrated that the nanofiber membrane with 6 wt% SiO₂ possessed notable properties, such as better thermal stability, higher porosity and electrolyte uptake, resulting in higher ionic conductivity (3.23×10^-3 S·cm^-1) when compared with pure PMIA nanofiber membrane. Significantly, the SiO2/PMIA nanofiber membrane based Li/LiCoO₂ cell exhibited more excellent cycling stability with capacity retention of 95 % after 50 cycles. The results indicated that the SiO₂-doped PMIA nanofiber membranes had a potential application as separator in high temperature resistance lithium-ion batteries.     

Comparision of the properties of UV-cured polyurethane acrylates containing different diisocyanates and low molecular weight diols

UV-curable polyurethane acrylate prepolymers were prepared from diisocyanates [isophorone diisocyanate (IPDI), 2,4-toluene diisocyanate (TDI), or 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI)], diols [ethylene glycol (EG), 1,4-butane diol (BD), or 1,6-hexane diol (HD)], polypropylene glycol as a polyol. UV-curable mixtures were formulated from the prepolymer (90 wt%), reactive diluent monomer trimethylol propane triacrylate (10 wt%), and photoinitiator 1-hydroxycyclohexyl ketone (3 wt% based on prepolymer/diluent). The effects of different diisocyanates/low molecular weigh diol on the dynamic mechanical thermal properties and elastic recovery of UV-cured polyurethane acrylate films were examined. The tensile storage modulus increased a little in the order of EG>BD>HD at the same diisocyanate. Two loss modulus peaks for all samples are observed owing to the glass transition of soft segments (T _gs ) and the glass transition temperature of hard segments (T _gh ). For the same diisocyanate,T _gs decreased, however,T _gh increased, in the order of HD>BD>EG. The elastic recovery also increased in the order of HD>BD>EG at the same diisocyanate. In case of same diols,T _gh increased in the order of H₁₂MDI>TDI>IPDI significantly. The ultimate elongation and elastic recovery increased in the order of TDI>IPDI>H₁₂MDI at the same diol.     

Nano-SiO2 filled rice husk/polypropylene composites: Physico-mechanical properties

In this research, reinforcing effect of hybrid filler including rice husk (RH), beech bark (BB) and nano-SiO₂, in polypropylene has been investigated. In the sample preparation, four levels of filler loading were used for waste lignocellulosic materials (55-58 wt.%) and nano-SiO₂ (0-4 wt.%). In order to increase the interphase adhesion, polypropylene grafted with maleic anhydride was added as a coupling agent to all the composites studied. The physical properties, viz. the thickness swelling and water absorption, and mechanical properties, namely, the tensile, flexural and notched Izod impact strengths, of the composites were determined. Generally, high amount of filler content in composites can lead to the reduction of interfacial adhesion between matrix polymer and filler, and it limits their applications. The results showed that while flexural properties and elongation at break were moderately improved by the increase in the amount of filler in the matrix, tensile and Izod impact strengths decreased dramatically. However, the composites had acceptable mechanical strength levels. The mechanical properties of composites filled with RH are generally greater than BB composites. The thickness swelling and water absorption of the composites increased with the increase in the filler loading, but to a negligible extent as compared with the wood-based composites and the solid woods. Nano-SiO₂ addition showed little positive effect on the mechanical properties. It can be concluded from this study that the used waste lignocellulosic materials are attractive reinforcements from the standpoint of their physico-mechanical properties.     

Preparation of the Multicomponent High Temperature Proton Exchange Membranes with Layer by Layer Self-assembly Technique

Layer by layer (LBL) self-assembly technique has been proved to be a feasible method that enables to accomplish the preparation of functional membranes with multilayered structure. In this research, the polymer of sulfonated polyetheretherketone (SPEEK) and thioglycolic acid capping of cadmium telluride (CdTe) nanocrystals as polyanion, the polymer of polyurethane (PU) as polycation have been used to prepare membrane electrolytes. These multilayered membranes showed good thermal stability and exhibited low liquid methanol permeability, which provided a possibility for the prepared membranes as proton exchange membranes (PEMs) to apply in direct methanol fuel cells (DMFCs). We have also demonstrated that the multicomponent (SPEEK/PU/CdTe/PU)₁₀₀ membranes favored to combine more phosphoric acid (PA) molecules and possessed a higher proton conductivity comparing to the bicomponent (SPEEK/PU)₂₁₀ membranes. So PA doped (SPEEK/PU/CdTe/PU)₁₀₀ membrane presented a maximum proton conductivity up to 8.6×10^-2 S/cm at 160 °C under anhydrous conditions. However, PA doped (SPEEK/PU)₂₁₀ membranes underwent a drop on proton conductivity while the temperature exceeded 120 °C.