Search Results (20)

Conductive polymer composites with a segregated structure are a promising route to obtaining electrically active materials at low filler loadings. In this work, aminated graphene (AmG) was used as a functional conductive filler for the fabrication of composites with a segregated structure based on polyvinyl chloride (PVC) and poly(vinylidene fluoride-co-tetrafluoroethylene) (P(VDF-TFE)). AmG was comprehensively characterized by electron microscopy, core-level and near-edge spectroscopy, optical spectroscopy, and electrical measurements. The synthesized AmG contained 14.34 at.% nitrogen, with amines accounting for 81.44% of the nitrogen-related spectral intensity, corresponding to an amine concentration of 11.78 at.%. AmG also exhibited a restored π-conjugated network, intrinsic conductivity of 20–33 S/cm, and a crumpled-flake morphology favorable for interfacial contact with polymer particles. At a filler loading of only 1 wt.%, the segregated composites reached electrical conductivity up to 1.3–1.4 × 10⁻⁴ S/cm, exceeding those of the unfilled polymers by seven orders of magnitude. At 11 GHz, the AmG-filled P(VDF-TFE) composite showed 15.1 dB attenuation for a theoretical thickness of 30 mm, transmitting no more than 3% of the incident radiation. These results identify AmG as a functional conductive filler for segregated electrically conductive polymer composites and demonstrate that the combination of amine-containing surface chemistry, restored electrical conductivity, and crumpled morphology enables conductive interparticle network formation in PVC- and P(VDF-TFE)-based composites at only 1 wt.% filler loading. Full article

Hydrothermally treated chitosan/polyvinyl alcohol beads (H-CS/PVA) were used as filler material in a fixed-bed column for continuous Cr (VI) removal. The effects of main operational parameters, namely bed height, initial concentration and flow rate, were evaluated in the respective ranges of 2–6 cm, 20–60 mg/L and 2.5–7.5 mL/min. Maximum removal efficiency and adsorption capacity were calculated as 64.2% and 15.53 mg/g, respectively. The corresponding breakthrough curves were analyzed by Yoon–Nelson, Adams–Bohart, Thomas and BDST (Bed Depth–Service Time) models, out of which the highest consistency was achieved with the Yoon–Nelson model for all studied conditions. The adsorbent maintained strong reusability, showing minimal loss (~2.5%) in desorption efficiency across three successive regeneration cycles with 0.1 M NaOH as the eluent. SEM and SEM–EDX analyses confirmed the presence of chromium on the H-CS/PVA surface at an elemental fraction of 1.03% (w.). Furthermore, FTIR and XPS analyses verified the role of amine and hydroxyl functionalities in the complexation and adsorption of Cr (VI). Overall, a column system operated under optimal conditions (H_bed: 6 cm, C₀: 40 mg/L, and column diameter: 2.5 cm) and regenerated three times can efficiently treat 20 L of Cr (VI)-contaminated wastewater, resulting in an associated environmental impact of 0.896 kg CO₂-eq. Full article

This study evaluated a biomimetic filler strategy for two-step universal dental adhesives by integrating amine-functionalized mesoporous silica nanoparticles (MSNs) loaded with polyacrylic acid-stabilized amorphous calcium phosphate (PA–ACP) into the primer phase. MSNs were synthesized and characterized by FTIR, N₂ sorption (BET), and HRTEM to confirm structural integrity and effective PA–ACP loading. Two commercial adhesives (G2 Bond and OptiBond eXTRa) were modified by incorporating different volumes fractions (10, 15, 20 vol%) of PA–ACP/MSN. Wettability (contact angle), microtensile bond strength (μTBS), and cytotoxicity (indirect MTT assay using human periodontal ligament fibroblasts, HPLFs) were assessed. The results demonstrated that incorporating up to 15 vol% PA–ACP/MSN maintained favorable wettability and bond strength, comparable to those of the unmodified controls. At 20 vol%, significant increases in contact angles and reductions in bond strength indicated impaired primer infiltration. Cytotoxicity testing confirmed high fibroblast viability (>70%) across all tested concentrations, verifying the biocompatibility of PA–ACP/MSN-filled primers. This work confirms the feasibility of a biomimetic adhesive design using PA–ACP/MSN in the primer phase without compromising immediate wettability and immediate μTBS up to 15 vol%. Remineralization is a potential capability that requires verification in future studies. Full article

Cellulose nanofibril (CNF) is a sort of novel nanomaterial directly extracted from plant resources, inheriting the advantages of cellulose as a cheap, green and renewable material for the development of new-generation eco-friendly electronics. In recent years, CNF-based triboelectric nanogenerator (TENG) has attracted increasing research interests, as the unique chemical, morphological, and electrical properties of CNF render the device with considerable flexibility, mechanical strength, and triboelectric output. In this study, we explore the use of isoreticular metal-organic frameworks (IRMOF) as functional filler to improve the performance of CNF based TENGs. Two types of IRMOFs that own the same network topology, namely IRMOF-1 and its aminated version IRMOF-3, are embedded with CNF to fabricated TENGs; their contribution to triboelectric output enhancement, including the roughness effect induced by large particles as well as the charge induction effect arisen from -NH₂ groups, are discussed. The performance-enhanced CNF-based TENG with 0.6 wt.% of IRMOF-3 is utilized to harvest mechanical energy from human activities and charge commercial capacitors, from which the electrical energy is sufficient to light up light-emitting diodes (LEDs) and drive low-power electronic devices. In addition, a locomotor analysis system is established by assembling the above TENGs and capacitors into a 3 × 3 sensing array, which allowed signal extraction from each sensing unit to display a motion distribution map. These results demonstrate the great potential of CNF/IRMOF-based TENGs for development of self-powered sensing devices for long-term motion monitoring. Full article

A nonterminal liquid crystal epoxy monomer is used to create an epoxy–amine network with a typical diamine 4,4′diaminodiphenylmethane. The plain matrix is compared to matrices modified with inorganic fillers: TiO₂ or SiO₂. Conditions of the curing reaction and glass transition temperatures in the cured products are determined through differential scanning calorimetry and broadband dielectric spectroscopy. The curing process is also followed through optical and electrical observations. The dielectric response of all investigated networks reveals a segmental α-process related to structural reorientation (connected to the glass transition). In all products, a similar process associated with molecular motions of polar groups also appears. The matrix modified with TiO₂ exhibits two secondary relaxation processes (β and γ). Similar processes were observed in the pure monomer. An advantage of the network with the TiO₂ filler is a shorter time or lower temperature required for optimal curing conditions. The physical properties of cured matrices depend on the presence of a nematic phase in the monomer and nonterminal functional groups in the aliphatic chains. In effect, such cured matrices can have more flexibility and internal order than classical resins. Additional modifiers used in this work shift the glass transition above room temperature and influence the fragility index in both cases. Full article

Materials with monolithic structures, such as epoxy monoliths, are used for a variety of applications, such as for column fillers in gas chromatography and HPLC, for separators in lithium-ion batteries, and for precursor polymers for monolith adhesion. In this study, we investigated the fabrication of epoxy monoliths using 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C) as the tetrafunctional epoxy and 4,4′-methylenebis(cyclohexylamine) (BACM) as the amine curing agent to control pore diameters using polyethylene glycols (PEGs) of differing molecular weights as the porogenic agents. We fabricated an epoxy monolith with micron-order pores and high strength levels, and which is suitable for the precursors of composite materials in cases where smaller PEGs are used. We discussed the effects of the porous structures of monoliths on their physical properties, such as tensile strength, elongation, elastic modulus, and glass transition temperatures. For example, epoxy monoliths prepared in the presence of PEGs exhibited an elastic modulus less than 1 GPa at room temperature and Tg values of 175–187 °C, while the epoxy bulk thermoset produced without any porogenic solvent showed a high elastic modulus as 1.8 GPa, which was maintained at high temperatures, and a high Tg of 223 °C. In addition, the unique adhesion characteristics of epoxy monolith sheets are revealed as a result of the combinations made with commercial epoxy and acrylic adhesives. Epoxy monoliths that are combined with conventional adhesives can function as sheet-type adhesives purposed with avoiding problems when only liquid-type adhesives are used. Full article

A one-pot, two-step process was developed for the preparation of pyrrole compounds from 2,5-dimethylfuran. The first step was the acid-catalyzed ring-opening reaction of 2,5-dimethylfuran (DF), leading to the formation of 2,5-hexanedione (HD). A stoichiometric amount of water and a sub-stoichiometric amount of sulfuric acid were used by heating at 50 °C for 24 h. Chemically pure HD was isolated, with a quantitative yield (up to 95%), as revealed by ¹H-NMR, ¹³C-NMR, and GC-MS analyses. In the second step, HD was used as the starting material for the synthesis of pyrrole compounds via the Paal–Knorr reaction. Various primary amines were used in stoichiometric amounts. ¹H-NMR, ¹³C-NMR, ESI-Mass, and GC-Mass analyses confirmed that pyrrole compounds were prepared with very good/excellent yields (80–95%), with water as the only co-product. A further purification step was not necessary. The process was characterized by a very high carbon efficiency, up to 80%, and an E-factor down to 0.128, whereas the typical E-factor for fine chemicals is between 5 and 50. Water, a co-product of the second step, can trigger the first step and therefore make the whole process circular. Thus, this synthetic pathway appears to be in line with the requirements of a sustainable chemical process. A pyrrole compound bearing an SH group (SHP) was used for the functionalization of a furnace carbon black (CB). The functionalized CB (CB/SHP) was utilized in place of silica, resulting in a 15% mass reduction of reinforcing filler, in an elastomeric composite based on poly(styrene-co-butadiene) from solution anionic polymerization and poly(1,4-cis-isoprene) from Hevea Brasiliensis. Compared to the silica-based composite, a reduction in the Payne effect of about 25% and an increase in the dynamic rigidity (E’ at 70 °C) of about 25% were obtained with CB/SHP. Full article

The increase in the global population has caused an increment in energy demand, and therefore, energy production has to be maximized through various means including the burning of natural gas. However, the purification of natural gas has caused CO₂ levels to increase. Hollow fiber membranes offer advantages over other carbon capture technologies mainly due to their large surface-to-volume ratio, smaller footprint, and higher energy efficiency. In this work, hollow fiber mixed matrix membranes (HFMMMs) were fabricated by utilizing cellulose triacetate (CTA) as the polymer and amine-functionalized metal-organic framework (NH₂-MIL-125(Ti)) as the filler for CO₂ and CH₄ gas permeation. CTA and NH₂-MIL-125(Ti) are known for exhibiting a high affinity towards CO₂. In addition, the utilization of these components as membrane materials for CO₂ and CH₄ gas permeation is hardly found in the literature. In this work, NH₂-MIL-125(Ti)/CTA HFMMMs were spun by varying the air gap ranging from 1 cm to 7 cm. The filler dispersion, crystallinity, and functional groups of the fabricated HFMMMs were examined using EDX mapping, SEM, XRD, and FTIR. From the gas permeation testing, it was found that the NH₂-MIL-125(Ti)/CTA HFMMM spun at an air gap of 1 cm demonstrated a CO₂/CH₄ ideal gas selectivity of 6.87 and a CO₂ permeability of 26.46 GPU. Full article

The valorization of tree bark through chemical treatment into valuable products, such as bark acid, leads to the formation of process residues with a high solids content. Since they are of natural origin and are able to be suspended in water and acid, research was carried out on the recycling of suberic acid residues (SAR) as a bi-functional component of binder mixtures in the production of plywood. The 5%–20% (5%–30% for curing time) mass content of SAR has been investigated with urea-formaldehyde (UF) resin of about 66% of dry content. The results show that the curing time of the bonding mixture can be reduced to about 38% and 10%, respectively, for hot and cold curing, of the initial curing time for the lowest SAR content. The decreasing curing time of the tested binder mixtures with the increase in SAR content was caused by the increasing amount of acidic filler, since amine resins as UF require acidification hardening, and the curing dynamics are strongly dependent, among others, on the content of the acid medium (curing agent). In the case of hot curing, a SAR content of about 20% allowed us to achieve the curing time of bonding mass with an industrial hardener. Investigations into the mechanical properties of examined panels showed a significant modulus of elasticity (MOE) increase with filler content increase. Similar conclusions can be drawn when analyzing the results of the modulus of rupture (MOR) investigations; however, these were only significant regarding hot-pressed samples. The shear strength of the plywood samples increased with the SAR rise for both cold- and hot-pressed panels. The in-wood damage of samples with SAR filler, hot-pressed, rose up to about 30% for the highest SAR filler content. For cold-pressed samples, no in-wood damage was found. The positive effect of veneer impregnation limiter by resin was identified for SAR acting as a filler. Moreover, a higher density of SAR-containing bonding lines was reached for hot-pressed panels. Therefore, the results confirmed the ability to use the SAR as an upcycled component of the bonding mixture for plywood production. Full article

There is a need to create next-generation polymer composites having high property, unique function, and intelligent behaviors, such as shape memory effect (SME) and self-healing (SH) capability. Rare earth complexes can provide luminescence for polymers, and their dispersion is highly affected by ligand structures. Here, we created three different REOCs with different ligands before studying the effects of ligands on REOC dispersion in polyurea–urethane (PUU) with disulfide bonds in main chains. In addition, the effects of different REOCs on mechanical properties, luminescent functions, and intelligent behaviors of PUU composites were studied. The results showed that REOC I (Sm(TTA)₃phen: TTA, thenoyltrifluoroacetone; phen, 1,10-phenanthroline) has incompatible ligands with the PUU matrix. REOC I and REOC III (Sm(BUBA)₃phen: BUBA, 4-benzylurea-benzoic acid) with amine and urea groups facilitate their dispersion. It was REOC III that helped the maintenance of mechanical properties of PUU composites due to the good dispersion and the needle-like morphologies. Due to more organic ligands of REOC III, the fluorescence intensity of composite materials is reduced. The shape recovery ratio of the composite was not as good as that of pure PUU when a large amount of fillers was added. Besides, REOC I reduced the self-healing efficiency of PUU composites due to poor dispersion, and the other two REOCs increased the self-healing efficiency. The results showed that ligands in REOCs are important for their dispersion in the PUU matrix. The poor dispersion of REOC I is unbeneficial for mechanical properties and intelligent behavior. The high miscibility of REOC II (Sm(PABA)₃phen: PABA, 4-aminobenzoic acid) decreases mechanical properties as well but ensures the good shape recovery ratio and self-healing efficiency. The mediate miscibility and needle-like morphology of REOC III are good for mechanical properties. The shape recovery ratio, however, was decreased. Full article

Silica fillers are used in various nanocomposites in combination with silanes as a reinforcing filler. In tire technology, silica is generally functionalized before (pre-treated) or during mixing (in-situ silanization or post-treated). In both cases, a soft base catalyst (e.g., triethylamine or diphenyl guanidine, DPG) is typically used to accelerate and increase the yield of the silane/silica coupling reaction. In this study, we investigated how pre-treatments of silica particles with either strong amine or hydride bases impact the silanization of silica prior to or during SBR mixing for silica-rubber nanocomposite fabrication. Our findings are supported by molecular characterization (solid state ²⁹Si NMR, ¹H NMR and TGA), and scanning electron microscopy. In addition, the impact of these silica pre-treatments on a nanocomposite’s mechanical properties was evaluated using dynamic mechanical analysis (DMA). Full article

CO₂ separation from raw natural gas can be achieved through the use of the promising membrane-based technology. Polymeric membranes are a known method for separating CO₂ but suffer from trade-offs between its permeability and selectivity. Therefore, through the use of mixed matrix membranes (MMMs) which utilizes inorganic or hybrid fillers such as metal-organic frameworks (MOFs) in polymeric matrix, the permeability and selectivity trade-off can be overcome and possibly surpass the Robeson Upper Bounds. In this study, various types of MOFs are explored in terms of its structure and properties such as thermal and chemical stability. Next, the use of amine and non-amine functionalized MOFs in MMMs development are compared in order to investigate the effects of amine functionalization on the membrane gas separation performance for flat sheet and hollow fiber configurations as reported in the literature. Moreover, the gas transport properties and various challenges faced by hollow fiber mixed matrix membranes (HFMMMs) are discussed. In addition, the utilization of amine functionalization MOF for mitigating the challenges faced is included. Finally, the future directions of amine-functionalized MOF HFMMMs are discussed for the fields of CO₂ separation. Full article

Currently, cellulose acetate (CA) membranes dominate membrane-based CO₂ separation for natural gas purification due to their economical and green nature. However, their lower CO₂ permeability and ease of plasticization are the drawbacks. To overcome these weaknesses, we have developed high-performance mixed matrix membranes (MMMs) consisting of cellulose triacetate (CTA), cellulose diacetate (CDA), and amine functionalized zeolitic imidazolate frameworks (NH₂-ZIF-8) for CO₂ separation. The NH₂-ZIF-8 was chosen as a filler because (1) its pore size is between the kinetic diameters of CO₂ and CH₄ and (2) the NH₂ groups attached on the surface of NH₂-ZIF-8 have good affinity with CO₂ molecules. The incorporation of NH₂-ZIF-8 in the CTA/CDA blend matrix improved both the gas separation performance and plasticization resistance. The optimized membrane containing 15 wt.% of NH₂-ZIF-8 had a CO₂ permeability of 11.33 Barrer at 35 °C under the trans-membrane pressure of 5 bar. This is 2-fold higher than the pristine membrane, while showing a superior CO₂/CH₄ selectivity of 33. In addition, the former had 106% higher CO₂ plasticization resistance of up to about 21 bar and an impressive mixed gas CO₂/CH₄ selectivity of about 40. Therefore, the newly fabricated MMMs based on the CTA/CDA blend may have great potential for CO₂ separation in the natural gas industry. Full article

In this study, defect-free facilitated transport mixed matrix membrane (MMM) with high loading amount of UiO-66-NH₂ nanoparticles as metal–organic frameworks (MOFs) was fabricated. The MOFs were covalently bonded with poly (vinyl alcohol) (PVA) to incorporate into a poly (vinyl amine) (PVAm) matrix solution. A uniform UiO-66-NH₂ dispersion up to 55 wt.% was observed without precipitation and agglomeration after one month. This can be attributed to the high covalent interaction at interfaces of UiO-66-NH₂ and PVAm, which was provided by PVA as a functionalized organic linker. The CO₂ permeability and CO₂/N₂ and selectivity were significantly enhanced for the fabricated MMM by using optimal fabrication parameters. This improvement in gas performance is due to the strong impact of solubility and decreasing diffusion in obtained dense membrane to promote CO₂ transport with a bicarbonate reversible reaction. Therefore, the highest amount of amine functional groups of PVAm among all polymers, plus the abundant amount of amines from UiO-66-NH₂, facilitated the preferential CO₂ permeation through the bicarbonate reversible reaction between CO₂ and –NH₂ in humidified conditions. XRD and FTIR were employed to study the MMM chemical structure and polymers–MOF particle interactions. Cross-sectional and surface morphology of the MMM was observed by SEM-EDX and 3D optical profilometer to detect the dispersion of MOFs into the polymer matrix and explore their interfacial morphology. This approach can be extended for a variety of polymer–filler interfacial designs for gas separation applications. Full article

In this study, graphene oxide (GO) nanosheets were modified with an amine functional group to obtain amine-functionalized graphene (AMG) nanosheets and then blended with the aniline curing agent of bisphenol-A (BPA) epoxy resin to crosslink BPA epoxy resin. The AMG-blended curing agent and BPA epoxy resin formed an intermolecular hydrogen bond that was stronger than the π–π stacking force between benzene rings of graphene nanosheets. Therefore, AMG nanosheets exhibited excellent dispersion in the aniline curing agent. The amine group of AMG-blended curing agents and the epoxy functional group of BPA epoxy resin exhibited strong chemical activity and underwent crosslinking and polymerization. AMG nanosheets were mixed with BPA epoxy resin to form a crosslinked structure through the epoxy ring-opening polymerization of the resin. The mechanical properties of the epoxy resin nanocomposites were significantly improved by the added 1 wt.% AMG nanosheets. The tensile strength was enhanced by 98.1% by adding 1 wt.% AMG in epoxy. Furthermore, the impact resistance of the epoxy resin was enhanced by 124.4% after adding 2.67 wt.% of AMG nanosheets. Compared with other reinforced fillers, AMG nanosheets are very light and can therefore be used as nanocomposite materials in coating applications, the automotive industry, aerospace sheet materials, wind power generation, and other fields. Full article