Preparation and Properties of UV-Curable Waterborne Polyurethane Acrylate/MXene Nanocomposite Films.

In this study, waterborne polyurethane acrylate (WPUA)/MXene nanocomposite films with varying MXene loadings were fabricated using UV-curing technology, where MXene (Ti3C2Tx) was employed as a nanofiller. The microstructure and chemical structure of the WPUA/MXene nanocomposite films were examined by XRD and FTIR, respectively. The water contact angle testing demonstrated that the incorporation of MXene into the nanocomposite films led to an increase in their hydrophilic properties. The tensile strength, the elongation at break, and Young's modulus of the WPUA/MXene nanocomposite coatings exhibited an initial increase followed by a decrease with increasing MXene loadings. Compared to the pure WPUA film, the tensile strength and elongation at break of nanocomposites with 0.077 wt% MXene loading reached their maximum values, which increased by 39.9% and 38.5%, respectively. Furthermore, the glass transition temperature and the thermal stability were both enhanced by MXene to some extent. This study introduces a novel method for utilizing MXene in UV-curable waterborne coatings.

Mechanical Properties of Low-Molecular-Weight Peptide Hydrogels Improved by Thiol-Ene Click Chemistry.

Low-molecular-weight peptide hydrogels can be formed by self-assembly through weak interactions, but the application of the hydrogel is influenced by its weak mechanical properties. Therefore, it is important to construct low-molecular-weight peptide hydrogels with excellent mechanical properties. In this work, we designed the pentapeptide molecule Fmoc-FFCKK-OH (abbreviated as FFCKK) with a sulfhydryl group, and another low-molecular-weight cross-linker N,N'-methylenebis(acrylamide) (MBA) was introduced to construct a hydrogel with excellent mechanical properties. The secondary structure change process of FFCKK and the assembly mechanism of hydrogel were analyzed using theoretical calculations and experimental characterizations. The occurrence of thiol-ene click chemistry provides covalent interaction in the hydrogel, and the synergistic effect ofcovalent interaction and hydrogen bonding improves the mechanical properties of the hydrogel by nearly 10-fold. The hydrogel was observed to be able to withstand a stress of 368 Pa and to break in a layer-by-layer manner by compression testing. The micromechanics of the hydrogels were characterized, and the excellent mechanical properties of the hydrogels were confirmed. The synergistic approach provides a new idea for the preparation of low-molecular-weight peptide hydrogels and facilitates the expansion of their potential applications in biomedical fields.

Preparation and Mechanical Properties of UV-Curable Epoxy Acrylate/Modified Aramid Nanofiber Nanocomposite Films.

In order to enhance the mechanical properties of UV-curable epoxy acrylate (EA)-based coatings, 3-(trimethoxysilyl)propyl methacrylate modified aramid nanofibers (T-ANFs) were synthesized and used as nanofillers to prepare EA/T-ANF nanocomposite films. The morphology of T-ANFs was characterized by transmission electron microscopy. The chemical structure of T-ANFs was analyzed via infrared spectroscopy, confirming successful grafting of methyl methacryloyloxy groups onto the surface of aramid nanofibers (ANFs). Real-time infrared spectroscopy was employed to investigate the influence of ANFs and T-ANFs on the photopolymerization kinetics of the EA film. The results revealed that the addition of ANFs and T-ANFs led to a decrease in the photopolymerization rate during the initial stage but had little impact on the final double bond conversion, with all samples exhibiting a conversion rate of over 83%. The incorporation of ANFs improved the tensile strength of the films while significantly reducing their Young's modulus. In contrast, the addition of T-ANFs led to a substantial increase in both tensile stress and Young's modulus of the films. For instance, the tensile strength and Young's modulus of the 0.1 wt% of T-ANF film increased by 52.7% and 41.6%, respectively, compared to the pure EA film. To further study the dispersion morphology and reinforcement mechanism, the cross-sectional morphology of the films was characterized by scanning electron microscopy.

Conductive Aramid Fibers from Electroless Silver Plating of Crosslinked HPAMAM-Modified PPTA: Preparation and Properties.

Conductive aramid (PPTA) fibers are highly needed for making flexible conductive materials, antistatic materials, and electromagnetic shielding materials. In this work, silver-plated conductive PPTA fibers with high conductivity and excellent mechanical properties were prepared by the electroless plating of PPTA fibers modified with crosslinked hyperbranched polyamide-amine (HPAMAM). The crosslinked HPAMAM creates a stable interface between the PPTA fibers and the silver plating. The morphology and physicochemical properties of the modified and the silver-plated fibers were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and thermogravimetric analysis. Three epoxy crosslinking agents with different chain lengths were used to crosslink HPAMAM, and the effects of HPAMAM concentration, crosslinking agent dosage, and crosslinking time on the resistance of the fibers were studied. The long chain crosslinking agent appears to be beneficial to silver plating. The lowest resistance (0.067 Ω/cm) was attained when HPAMAM was modified by diethylene glycol diglycidyl ether (1:1 molar ratio), and 20 g/L HPAMAM was used to modify the PPTA fibers. The tensile strength of the original PPTA fibers decreased by only 3% or less after silver plating.

Facile Synthesis of Cross-linked Hyperbranched Polyamidoamines Dendrimers for Efficient Hg(â ¡) Removal From Water.

Dendrimers as commonly used metal ions adsorption materials have the advantages of good adsorption performance and high reuse rate, but the high cost limits its extensive use. Compared with dendrimers, hyperbranched dendrimers have similar physical and chemical properties and are more economical. Therefore, hyperbranched dendrimers are more suitable for industrial large-scale adsorption. The hyperbranched polyamidoamine (HPAMAM) gels were prepared by cross-linking hyperbranched polyamidoamine (HPAMAM-ECH-x and HPAMAM-EGDE-x) with different amounts of epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE), respectively. The as-synthesized adsorbents were characterized by FT-IR, SEM and XPS. The prepared adsorbents were used to adsorb Hg(Ⅱ) in aqueous solution, and the effects of solution pH, contact time, temperature and initial concentration of metal ion on the adsorption capacity were investigated. The effect of solution pH indicated that the optimum condition to Hg(Ⅱ) removing was at pH 5.0. The adsorption kinetic curves of the two kinds of materials were in accordance with the pseudo-second-order model. For the HPAMAM-ECH samples, the adsorption thermodynamic curves fitted the Langmuir model, while for the HPAMAM-EGDE samples, both Langmuir and Freundlich equations fitted well. The maximum adsorption capacity of HPAMAM-ECH-3 obtained from Langmuir model toward Hg(Ⅱ) was 3.36 mmol/g at pH 5.0 and 35°C.

Fabrication of Triethylenetetramine Terminal Hyperbranched Dendrimer-Like Polymer Modified Silica Gel and Its Prominent Recovery Toward Au (III).

To further increase the quantity and density of functional groups on adsorbent, terminal triethylenetetramine hyperbranched dendrimer-like polymer modified silica-gel (SG-TETA and SG-TETA2) was synthesized. The hyperbranched dendrimer-like polymer was successfully introduced onto silica gel and new cavities were formed, which was demonstrated by FTIR, SEM, and BET. The highest adsorption capacities of SG-TETA and SG-TETA2 obtained from Langmuir model toward Au(III) were 2.11, and 2.27 mmol g-1, respectively, indicating that SG-TETA2 possessing more functional groups had a better adsorption ability. Moreover, the adsorbents combined with Au(III) ion through chelation and electrostatic attraction mechanism, after which reduction reactions for Au(III) ion loaded on adsorbents proceeded. SG-TETA2 had better adsorption selectivity than SG-TETA in removing Au(III) in Au-existed ion solution systems. SG-TETA2 had higher overall adsorption capacities compared to silica-gel-based hyperbranched polymers functionalized by diethylenetriamine. Therefore, the effective recovery makes SG-TETA2 a practical adsorbent in removing Au(III) ion from e-wastes and industrial effluents with much prospect.

Amino- and Thiol- Polysilsesquioxane Simultaneously Coating on Poly(p-Phenylenetherephthal Amide) Fibers: Bifunctional Adsorbents for Hg(II).

A double reagents simultaneous functionalization (DRSF) was used to prepare porous polysilsesquioxane with NH2 and SH bifunctional groups (PAMPSQ) coated poly(p-phenylenetherephthal amide) (PPTA) fibers adsorbents (PPTA-AM), via in situ condensations with aminopropyltriethoxysilane (APTES) and mercaptopropyltriethoxysilane (MPTES). The PAMPSQ coated on the PPTA surface was in the form of nanoparticles and its morphology varied with the proportion of the reactants. The PAMPSQ exhibited loose open meso- or macroporous features. The functional groups utilization of PAMPSQ was much higher than those of polysilsesquioxane on the mono-functional adsorbents with thiol or amino groups. The selective adsorption of PPTA-AM adsorbents for Hg(II) in binary component metal ion systems indicated their potential application in environmental remediation. The adsorption mechanism of Hg(II) onto PPTA-AM was proposed.

Aramid Nanomaterials of Various Morphologies: Preparation and Mechanical Property Enhancement.

Aramid nanofibers (ANFs) are a novel type of promising nanoscale building blocks for high-performance nanocomposites. Conventionally, ANFs are used to composite with polymers containing polar groups such as -OH and -NH2 since those polymers can interact with the amide groups in ANFs through polar-polar interaction such as hydrogen bonding. In this study, ANFs were derivatized with non-polar alkyl groups including ethyl, octyl and dodecyl groups and used as a performance-enhancing additive to polyvinyl chloride (PVC) with weak polarity. Interestingly, it was observed that the morphologies of the resulting alkyl-derivatized aramid nanomaterials (R-ANMs) varied significantly including nanofibers, nanobranches, nanosheets, and nanospheres, all of which depended on the degree of substitution (DS) and the chain length of the alkyl group. As an additive, R-ANMs improved the Young's modulus, toughness and yield strength of the PVC films. This study proves the concept that ANFs can be used to composite weakly polar or non-polar polymers.

Pore structure control factors of polyamine-bridged polysilsesquioxanes by sol-gel method and their structure-adsorption properties for Au(III).

A series of bridged polysilsesquioxane (BPS) materials was synthesized by the sol-gel method from 3-chloropropyl trimethoxysilane, diethylenetriamine (DETA) or ethylenediamine. Tetraethyl orthosilicate (TEOS) and/or one of the two templates, hexadecyl trimethyl ammonium bromide (CTAB) or P123, were used in the co-condensation process to construct some of the porous adsorbents. The adsorption of Au(III) was the highest for samples without TEOS, especially for the DETA series with CTAB template. This study elucidates the synthesis and applications of BPS materials.

Hg(II) adsorption using amidoximated porous acrylonitrile/itaconic copolymers prepared by suspended emulsion polymerization.

Initially, porous acrylonitrile/itaconic acid copolymers (AN/IA) were prepared by suspended emulsion polymerization. Successively, the cyano groups in AN/IA copolymers were converted to amidoxime (AO) groups by the reaction with hydroxylamine hydrochloride. The structures of the AN/IA and amidoximated AN/IA (AO AN/IA) were characterized by infrared spectroscopy, scanning electron microscopy, and porous structural analysis. The adsorption properties of AO AN/IA for Hg(II) were investigated. The results show that AO AN/IA has mesopores and macropores, and surface area of 11.71 m(2) g(-1). It was found that AO AN/IA has higher affinity for Hg(II), with the maximum adsorption capacity of 84.25 mg g(-1). The AO AN/IA also can effectively remove Hg(II) from different binary metal ion mixture systems. Furthermore, the adsorption kinetics and thermodynamics were studied in detail. The adsorption equilibrium can quickly be achieved in 4 h determined by an adsorption kinetics study. The adsorption process is found to belong to the second-order model, and can be described by the Freundlich model.

Synthesis of silica gel supported salicylaldehyde modified PAMAM dendrimers for the effective removal of Hg(II) from aqueous solution.

A series of silica gel supported salicylaldehyde modified PAMAM dendrimers (SiO2-G0-SA ∼ SiO2-G2.0-SA) were synthesized and their structures were characterized by FTIR, XRD, SEM, TGA, and porous structure analysis. The feasibility of these adsorbents for the removal of Hg(II) from aqueous solution was first described and the adsorption mechanism was proposed. The adsorption was found to depend on solution pH, the generation number of salicylaldehyde modified PAMAM dendrimers, contact time, temperature, and initial concentration. Results showed that the optimal pH was about 6 and the adsorption capacity increased with the increasing of generation number. Density functional theory (DFT) method was used to investigate the coordination geometries and the chelating mechanism. Adsorption kinetics was found to follow the pseudo-second-order model with film diffusion process as rate controlling step. Adsorption isotherms revealed that adsorption capacities increased with the increasing of temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models were employed to analyze the equilibrium data. The adsorption can be well described by Langmuir isotherm model and took place by chemical mechanism. The thermodynamics properties indicated the adsorption processes were spontaneous and endothermic nature. The maximum adsorption capacity of SiO2-G0-SA, SiO2-G1.0-SA, and SiO2-G2.0-SA were 0.91, 1.52, and 1.81 mmol g(-1), respectively. The considerable higher adsorption capacity compared with other adsorbents indicates SiO2-G0-SA ∼ SiO2-G2.0-SA are favorable and useful for the uptake of Hg (II), and can be potentially used as promising adsorbents for the effective removal of Hg(II) from aqueous solution.

Adsorption of Pb(II) from aqueous solution by silica-gel supported hyperbranched polyamidoamine dendrimers.

The adsorption properties of silica-gel supported hyperbranched polyamidoamine dendrimers (SiO(2)-G0-SiO(2)-G4.0) have been investigated by batch method. The effect of pH of the solution, contact time, initial Pb(II) ion concentration, temperature and coexisting metal ions have been demonstrated. The results indicated that the optimum pH value was 5. Adsorption kinetics was found to follow the pseudo-second-order model and controlled by film diffusion. The adsorption isotherms were fitted by Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherm models. Langmuir isotherm model was found to be more suitable to describe the equilibrium data, suggesting the uptake of Pb(II) ions by monolayer adsorption. From D-R isotherm model, the calculated mean free energy E demonstrated the adsorption processes occurred by chemical ion-exchange mechanism. FTIR analysis revealed that amine groups were mainly responsible for the adsorption of Pb(II) by amino-terminated adsorbents, while CO of ester groups also participated in the adsorption process of ester-terminated ones. The adsorbents can selectively adsorb Pb(II) from binary ion systems in the presence of Mn(II), Cu(II), Co(II), and Ni(II). Based on the results, it is concluded that SiO(2)-G0-SiO(2)-G4.0 had great potential for the removal of Pb(II) from aqueous solution.

Synthesis of porous acrylonitrile/methyl acrylate copolymer beads by suspended emulsion polymerization and their adsorption properties after amidoximation.

Porous acrylonitrile (AN)/methyl acrylate (MA) copolymer beads were prepared by suspended emulsion polymerization. The cyano groups in AN/MA copolymer beads were converted to amidoxime (AO) groups by reaction with hydroxylamine hydrochloride (NH(2)OH.HCl) to remove metal ions in aqueous solution. The untreated AN/MA and amidoximated AN/MA (AO AN/MA) copolymer beads were characterized by FTIR spectroscopy, SEM, and porous structural analysis. Both mesopores and macropores were presented in AN/MA and AO AN/MA copolymer beads. Qualitative experiments of adsorption were conducted to evaluate modified and unmodified resins on fixing Hg(2+), Ag(+), Cu(2+), Fe(3+) and Pb(2+) from aqueous solution using batch extractions. It was found that AO AN/MA copolymer beads have excellent adsorption capacities for Hg(2+), Ag(+) and Cu(2+), especially for Hg(2+), and it have good selectivity for Hg(2+). The equilibrium was established in 10h through adsorption kinetics study. The Langmuir model was much better than the Freundlich model to describe the isothermal process.

Adsorption behaviors of Hg(II) on chitosan functionalized by amino-terminated hyperbranched polyamidoamine polymers.

The adsorption behaviors of Hg(II) on adsorbents, chitosan functionalized by generation 1.0-3.0 of amino-terminated hyperbranched polyamidoamine polymers (denoted as CTS-1.0, CTS-2.0 and CTS-3.0, respectively), were studied. The optimum pH corresponding to the maximum adsorption capacities was found to be 5.0 for the three adsorbents. The experimental equilibrium data of Hg(II) on the three adsorbents were fitted to the Freundlich and the Langmuir models, and it is found that the Langmuir isotherm was the best fitting model to describe the equilibrium adsorption. The kinetics data indicated that the adsorption process of Hg(II) ions on CTS-1.0, CTS-2.0 and CTS-3.0 were governed by the film diffusion and followed pseudo-second-order rate model. Thermodynamic analysis and FTIR analysis revealed that the adsorption behaviors of Hg(II) ions on the three adsorbents could be considered as spontaneous, endothermic and chemical sorption process, resulting in their higher adsorption capacities at higher temperature.

Removal and recovery of Hg(II) from aqueous solution using chitosan-coated cotton fibers.

Two types of chitosan-coated cotton fibers (SCCH and RCCH) were applied to remove and recover Hg(II) ions in aqueous solution. The adsorption kinetics and isotherms of the two fibers for Hg(II) were investigated at different temperatures. The results revealed that the adsorption kinetic processes of SCCH and RCCH fibers for Hg(II) followed the pseudo second-order model at lower temperatures and the pseudo first-order model at higher temperatures. Both the Langmuir and Freundlich models well described the adsorption isotherms of SCCH and RCCH fibers for Hg(II) in the temperature range studied. SCCH and RCCH fibers selectively adsorbed Hg(II) from binary ion systems in the presence of Pb(II), Cu(II), Ni(II), Cd(II), Zn(II), Co(II), Mn(II) and Ag(I). Increased temperature was beneficial to adsorption. The recovery of Hg(II) from aqueous solutions was also studied as a function of sample flow rate and volume, concentration and volume of eluent, elution rate, quantity of adsorbents added and concomitant ions. The results showed that the two fibers efficiently enriched and recovered Hg(II) in the presence of alkali and alkaline earth metals and some heavy metals under optimum conditions. The RCCH fiber exhibited better stability than the SCCH fiber following repeated use.

Comparison of synthesis of chelating resin silica-gel-supported diethylenetriamine and its removal properties for transition metal ions.

Four kinds of silica-gel (SG)-supported diethylenetriamine (DETA) chelating resins SG-DETA-1, SG-DETA-2, SG-DETA-3, and SG-DETA-4 were prepared by functionalization of silica-gel via so-called "heterogeneous-direct-amination" (hetero-DA), "homogeneous-direct-amination" (homo-DA), "heterogeneous end-group protection" (hetero-EGP), and "homogeneous end-group protection" (homo-EGP) routes, respectively. These functionalized reactions on silica-gel were confirmed through elemental analysis, infrared spectroscopy, X-ray diffractometry, porous analysis, and thermogravimetry. Element analysis revealed that the direct-amination routes and homogeneous condition were more beneficial than the corresponding end-group protection routes and heterogeneous condition to the syntheses of chelating resins with high N content. Several metal ions, such as Ag(+), Cu(2+), Ni(2+), Hg(2+), Zn(2+) and Pb(2+), were chosen as representatives to investigate the relationship between adsorption capacities and N content of ligands onto the surface of silica-gel. The experiments results showed that all resins, SG-DETA-1, SG-DETA-2, SG-DETA-3 and SG-DETA-4, had a better adsorption for Hg(2+) and Cu(2+) than others. One conclusion should be drawn from the above compared experiments, that is, higher N content of silica-gel resins does not ensure a higher utilization ratio of N.

Thermodynamics and kinetics of Zn(II) adsorption on crosslinked starch phosphates.

Crosslinked starch phosphates (CSP) with different contents of phosphate groups were used to adsorb Zn(II) from aqueous solution. Effects of adsorption time, initial concentration of Zn(II) ion, and temperature on the adsorption of Zn(II) by CSP were studied, and the equilibrium, thermodynamics and kinetics of the adsorption process were further investigated. It showed that crosslinked starch phosphates can effectively remove Zn(II) from the solution. The adsorption equilibrium data correlate well with the Langmuir isotherm model with a maximum adsorption capacity of 2.00mmolg(-1). The adsorption of Zn(II) on CSP is endothermic in nature. The pseudo-first-order and pseudo-second-order kinetic models were applied to test the experimental data. The pseudo-second-order kinetic model provided a better correlation of the experimental data in comparison with the pseudo-first-order model.

Degradation behavior of chitosan chains in the 'green' synthesis of gold nanoparticles.

The degradation behavior of chitosan chains in the synthesis of Au nanoparticles by a 'green' method was investigated in this paper for the first time. UV-vis absorption spectra suggested the formation of Au nanoparticles and TEM images showed that their sizes were between 10 and 50nm. During the process of synthesis, the intrinsic viscosity [eta] of chitosan was observed to decrease gradually, implying that the chitosan chains degraded under the reaction conditions. Further studies showed that the degree of degradation of the chitosan chains was changed with different reaction temperatures, reactant ratios, and the molecular weights of chitosan.

Preparation and metal-binding behaviour of chitosan functionalized by ester- and amino-terminated hyperbranched polyamidoamine polymers.

A series of insoluble chitosan (CTS) derivatives were prepared by grafting ester- and amino-terminated dendrimer-like polyamidoamine (PAMAM) into CTS using a divergent method by repeating two processes: (1) Michael addition of methyl acrylate (MA) to surface amino groups, and (2) amidation of the resulting esters with ethylenediamine (EDA). Their structures were characterized by infrared spectra (IR) and wide-angle X-ray diffraction (WAXD). The adsorption capabilities of the products for Au(3+), Pd(2+), Pt(4+), Ag(+), Cu(2+), Zn(2+), Hg(2+), Ni(2+), and Cd(2+) were studied. The results showed that the products exhibited better adsorption capabilities for Au(3+) and Hg(2+) than for other metal ions, and the adsorption capabilities of amino-terminated products were higher than those of ester-terminated ones. Also it was observed that a high percentage of grafting of PAMAM into CTS does not ensure a high adsorption capacity.

A chelating resin with bis[2-(2-benzothiazolylthioethyl)sulfoxide]: Synthesis, characterization and properties for the removal of trace heavy metal ion in water samples.

A new chelating resin containing bis[2-(2-benzothiazolylthioethyl)sulfoxide] was synthesized using chloromethylated polystyrene as material and characterized by elemental analysis and infrared spectra. The adsorption capacities of the newly formed resin for Hg(2+), Ag(+), Cu(2+), Zn(2+), Pb(2+), Mn(2+), Ni(2+), Cd(2+) and Fe(3+) were investigated over the pH range 1.0-6.0. The resin exhibited no affinity for alkali or alkaline earth metal ions. The maximum adsorption capacities of the resin for Hg(2+), Ag(+), Cu(2+), Zn(2+), Pb(2+), Mn(2+), Ni(2+), Cd(2+) and Fe(3+) were 1.49, 0.96, 0.58, 0.11, 0.37, 0, 0.24, 0.36 and 0.25mmolg(-1), respectively. In column operation it had been observed that Hg(2+) and Ag(+) in trace quantity could be separated from different binary mixtures and Hg(2+) could be effectively removed from industrial wastewater and the natural water spiked with Hg(2+) at usual pH.