Miracle-dz/UniFAR-FTUs huggingface dataset:
Electrostatic-Interaction-Driven Assembly of Binary Hybrids towards Fire-Safe Epoxy Resin Nanocomposites

Manganese dioxide (MnO2), as a promising green material, has recently attracted considerable attention of researchers from various fields. In this work, a facile method was introduced to prepare binary hybrids by fabricating three-dimensional (3D) zinc hydroxystannate (ZHS) cubes on two-dimensional (2D) MnO2 nanosheets towards excellent flame retardancy and toxic effluent elimination of epoxy (EP) resin. Microstructural analysis confirmed that the morphologies and structures of MnO2@ZHS binary hybrids were well characterized, implying the successful synthesis. Additionally, the morphological characterization indicated that MnO2@ZHS binary hybrids could achieve satisfactory interfacial interaction with the EP matrix and be well dispersed in nanocomposites. Cone calorimeter test suggested that MnO2@ZHS binary hybrids effectively suppressed the peak of heat release rate and total heat release of EP nanocomposites, performing better than MnO2 or ZHS alone. Condensed-phase analysis revealed that MnO2@ZHS binary hybrids could promote the char density and graphitization degree of char residues and thereby successfully retard the permeation of oxygen and flammable gases. Moreover, through the analysis of gas phase, it can be concluded that MnO2@ZHS binary hybrids could efficiently suppress the production of toxic gases during the degradation of EP nanocomposites. This work implies that the construction of 2D/3D binary hybrids with an interfacial interaction is an effective way to fabricate high-performance flame retardants for EP.
Antimony Removal from Water by a Chitosan-Iron(III)[ChiFer(III)] Biocomposite

The presence of antimony(III) in water represents a worldwide concern, mainly due to its high toxicity and carcinogenicity potential. It can be separated from water by the use of sustainable biopolymers such as chitosan or its derivatives. The present study applied chitosan modified with iron(III) beads to Sb(III) removal from aqueous solutions. The resulting material performed with a high adsorption capacity of 98.68 mg/g. Material characterization consisted of Raman spectroscopy (RS), X-ray diffraction (XRD), scanning electron microscope observations (SEM-EDX), Fourier transform infrared spectroscopy (FTIR) and point of zero charge (pHpzc). The adsorption study included pH study, effect of initial concentration, kinetics, ion effect, and reusability assessment. The RS, XRD, and FTIR results indicated that the main functional groups in the composite were related to hydroxyl and amino groups, and iron oxyhydroxide species of α-FeO(OH). The pHpzc was found to be 7.41. The best adsorption efficiency was set at pH 6. The equilibrium isotherms were better fitted with a non-linear Langmuir model, and the kinetics data were fitted with a pseudo-second order rate equation. The incorporation of iron into the chitosan matrix improved the Sb(III) uptake by 47.9%, compared with neat chitosan (CS). The material did not exhibit an impact in its performance in the presence of other ions, and it could be reused for up to three adsorption–desorption cycles.
Hyperbranched Polysiloxanes Based on Polyhedral Oligomeric Silsesquioxane Cages with Ultra-High Molecular Weight and Structural Tuneability

Hyperbranched siloxane-based polymers with ultra-high molecular weight were synthesized by the Piers–Rubinsztajn reaction between octakis(dimethylsiloxy) octasilsesquioxane with different dialkoxysilanes, using tris(pentafluorophenyl) borane as the catalyst. The origin of the high molecular weight is explained by the high reactivity of the catalyst and strain energy of isolated small molecule in which all eight silane groups close into rings on the sides of a single cubic cage. The structural tuneability was further demonstrated by use of methyl(3-chloropropyl)diethoxysilane, which generates a polymer with similar ultra-high molecular weight. Introduction of phosphonate groups through the chloropropyl sites later leads to functionalized polymers which can encapsulate various transition metal nanoparticles.
Anti-Fouling and Anti-Bacterial Modification of Poly(vinylidene fluoride) Membrane by Blending with the Capsaicin-Based Copolymer

Membrane fouling induced by the adsorption of organic matter, and adhesion and propagation of bacteria onto the surfaces, is the major obstacle for the wide application of membrane technology. In this work, the capsaicin-based copolymer (PMMA-PACMO-Capsaicin) was synthesized via radical copolymerization using methyl methacrylate (MMA), N-acrylomorpholine (ACMO) and 8-methyl-N-vanillyl-6-nonenamide (capsaicin) as monomers. Subsequently, the capsaicin-based copolymer was readily blended with PVDF to fabricate PVDF/PMMA-PACMO-Capsaicin flat sheet membrane via immersed phase inversion method. The effects of copolymer concentration on the structure and performance of resultant membranes were evaluated systematically. With increase of PMMA-PACMO-Capsaicin copolymer concentration in the casting solution, the sponge-like layer at the membrane cross-section transfers to macroviod, and the pore size and porosity of membranes increase remarkably. The adsorbed bovine serum albumin protein (BSA) amounts to PVDF/PMMA-PACMO-Capsaicin membranes decrease significantly because of the enhanced surface hydrophilicty. During the cycle filtration of pure water and BSA solution, the prepared PVDF/PMMA-PACMO-Capsaicin membranes have a higher flux recovery ratio (FFR) and lower irreversible membrane fouling ratio (Rir), as compared with pristine PVDF membrane. PVDF/PMMA-PACMO-Capsaicin membrane is found to suppress the growth and propagation of Staphylococcus aureus bacteria, achieving an anti-bacterial efficiency of 88.5%. These results confirm that the anti-fouling and anti-bacterial properties of PVDF membrane are enhanced obviously by blending with the PMMA-PACMO-Capsaicin copolymer.
Thickness-Dependent DC Electrical Breakdown of Polyimide Modulated by Charge Transport and Molecular Displacement

Polyimide has excellent electrical, thermal, and mechanical properties and is widely used as a dielectric material in electrical equipment and electronic devices. However, the influencing mechanism of sample thickness on electrical breakdown of polyimide has not been very clear until now. The direct current (DC) electrical breakdown properties of polyimide as a function of thickness were investigated by experiments and simulations of space charge modulated electrical breakdown (SCEB) model and charge transport and molecular displacement modulated (CTMD) model. The experimental results show that the electrical breakdown field decreases with an increase in the sample thickness in the form of an inverse power function, and the inverse power index is 0.324. Trap properties and carrier mobility were also measured for the simulations. Both the simulation results obtained by the SCEB model and the CTMD model have the inverse power forms of breakdown field as a function of thickness with the power indexes of 0.030 and 0.339. The outputs of the CTMD model were closer to the experiments. This indicates that the displacement of a molecular chain with occupied deep traps enlarging the free volume might be a main factor causing the DC electrical breakdown field of polyimide varying with sample thickness.
Investigation of the Viscoelastic Behavior Variation of Glass Mat Thermoplastics (GMT) in Compression Molding

Compression molding is a lightweight technology that allows to preserve fiber length and retain better mechanical properties compared to injection molding. In compression molding development, a suitable material such as glass fiber mat thermoplastics (GMT) is often used. However, because of the complicated micro-structure of the fibers and the fiber–resin matrix interactions, it is still quite challenging to understand the mechanism of compression molding and it is very difficult to obtain a uniformly compressed GMT product. In this study, we propose a method to measure the rheological properties of GMT through a compression system. Specifically, we utilized a compression molding system to record the relation between the loading force and the displacement. This quantitative information was used to estimate the power-law index and viscoelastic parameters and predict viscosity. Moreover, the estimated viscoelastic parameters of GMT were implemented into Moldex3D to evaluate the flow behavior under compression. The results showed that the trend of the loading force variation was consistent in numerical simulation and experiments. However, at the final stage of compression molding, the experimental loading force was much higher than that estimated by simulation. To find out the mechanism causing this deviation, a series of studies were performed. Through TGA measurement, we found that the fiber content of the center portion of the compressed part increased from 63% to 85% during compression. This was expected, as a result of the fiber–polymer matrix separation effect. This fiber–polymer matrix separation effect influenced the power-law index and rheological parameters of GMT, making them fluctuate. Specifically, the power-law index changed from 1.0 to 0.62. These internal changes of the rheological properties further induced a much higher loading force in the real experimental GMT system. We further verified the rheological properties variation using pure polyamide (PA) and found that since there is no fiber–polymer matrix interactions the power-law index and curve-fitting rheological parameters were almost constant. The mechanism causing the deviation was therefore validated.
Highly Sensitive Detection of Melamine Based on the Fluorescence Resonance Energy Transfer between Conjugated Polymer Nanoparticles and Gold Nanoparticles

Adding melamine as additives in food products will lead to many diseases and even death. However, the present techniques of melamine detection require time-consuming steps, complicated procedures and expensive analytical apparatus. The fluorescent assay method was facile and highly sensitive. In this work, a fluorescence resonance energy transfer (FRET) system for melamine detection was constructed based on conjugated polymer nanoparticles (CPNs) and gold nanoparticles (AuNPs). The energy transfer efficiency is up to 82.1%, and the system is highly selective and sensitive to melamine detection with a lower detection limit of 1.7 nmol/L. Moreover, the interaction mechanism was explored. The results showed that the fluorescence of CPNs were firstly quenched by AuNPs, and then restored after adding melamine because of reducing FRET between CPNs and AuNPs. Lastly, the proposed method was carried out for melamine detection in powdered infant formula with satisfactory results.
A Roadmap towards Successful Nanocapsule Synthesis via Vesicle Templated RAFT-Based Emulsion Polymerization

Vesicle templated emulsion polymerization is a special form of emulsion polymerization where the polymer is grown from the outside of the vesicle, leading to nanocapsules. Cost effective nanocapsules synthesis is in high demand due to phasing out of older methods for capsule synthesis. Although the first indications of this route being successful were published some 10 years ago, until now a thorough understanding of the parameters controlling the morphologies resulting from the template emulsion polymerization was lacking. Most often a mixture of different morphologies was obtained, ranging from solid particles to pro-trusion structures to nanocapsules. A high yield of nanocapsules was not achieved until now. In this paper, the influence of initial vesicle dispersion, choice of the Reversible Addition-Fragmentation chain Transfer (RAFT) species and oligomer, monomer and crosslinker have been investigated. It turns out that good initial vesicle dispersion, molecular control of the RAFT process, a not too hydrophobic monomer and some crosslinking is needed to result in high yield of nanocapsules. In previous work, the level of RAFT control was often suboptimal and not properly verified and although nanocapsules were shown, other morphologies were also present. We now believe we have a full understanding of vesicle templated nanocapsules synthesis, relevant to many applications.
Castor Oil-Based Polyurethane Resin for Low-Density Composites with Bamboo Charcoal

Polyurethane (PU) foam adhesives were prepared from castor oil as a polyol with isocyanate poly(4,4’-methylene diphenyl isocyanate) (PMDI) using a solvent-free process. The NCO/OH molar ratio used for the preparation of PU foams was 1.5. Water, organosiloxane and dibutyltin dilaurate were used as the blowing agent, surfactant and catalyst, respectively. The ratio of blowing agent and catalyst were adjusted to optimize the properties. The results show that PU foam prepared with 4 wt % of castor oil catalyst and blowing agent has minimal water absorption and maximal volume expansion in the PU foams. FT-IR analysis shows that a urethane bond was formed by the hydroxyl group of castor oil and the –NCO group of isocyanate PMDI. More blowing agent and catalyst could improve the volume expansion ratio and reduce water retention of PU foams. It was found that Moso bamboo charcoal (Phyllostachys pubescens) and China fir wood particle (Cunninghamia lanceolate) composites with setting densities of 500 and 600 kg/m3 can be prepared from optimized castor oil-based PU foam adhesive at 100 °C for 5 min under a pressure of 1.5 MPa. Increasing the amount of bamboo charcoal decreases the equilibrium moisture content, water absorption and internal bonding strength of the composite. Notably, bamboo charcoal composite exhibits excellent dimensional stability. The optimized density and bamboo charcoal percentages of the composite were 500 kg/m3 and 50–100%, respectively. The castor oil-based PU composites containing bamboo charcoal fulfilled the CNS 2215 standards for particleboard. This dimensionally stable, low-density bamboo charcoal composite has high potential to replace current indoor building materials.
Incorporation of Tannic Acid in Food-Grade Guar Gum Fibrous Mats by Electrospinning Technique

The use of polysaccharides to produce functional micro- or nanoscale fibrous mats has attracted growing interest for their food-grade applications. In this study, the characterization and electro-spinnability of guar gum (GG) solutions loaded with tannic acid (TA) was demonstrated. Food-grade antioxidant materials were successfully produced by electrospinning while incorporating different loads of TA into GG fibers. Bead-free GG-TA fibers could be fabricated from GG solution (2 wt %) with 10 wt % TA. Increasing the amount of TA led to fibers with defects and larger diameter sizes. Fourier Transformed Infrared Spectroscopy and X-ray Diffraction of neat GG and TA loaded GG fibrous mats suggested that inclusion of TA interrupted the hydrogen bonding and that a higher density of the ordered junction zones formed with the increased TA. The high TA incorporation efficiency and retained antioxidant activity of the fibrous mats afford a potential application in active edible film or drug delivery system.
Comparative Studies on Two-Electrode Symmetric Supercapacitors Based on Polypyrrole:Poly(4-styrenesulfonate) with Different Molecular Weights of Poly(4-styrenesulfonate)

Poly(4-styrenesulfonate)-conducting polymer (PSS-CP) is advantageous for thin-film electrode manufacturing due to its high conductivity, high charge storage, structural stability, and excellent ink dispersion. In this work, comparative studies of two-electrode symmetric supercapacitors using Polypyrrole:Poly(4-styrenesulfonate) (PPy:PSS), with different molecular weights (Mw’s) of Poly(4-styrenesulfonate) (PSS) as the electrodes, were performed. PPy:PSS can be easily prepared using a simple solution process that enables the mass production of thin-film electrodes with improved electrical and electrochemical properties. As-prepared PPy:PSS, with different PSS molecular weights, were assembled into two-electrode supercapacitors based on coin cell structures. It was confirmed that the electrical and electrochemical properties of PPy:PSS were improved with increasing PSS molecular weight. The coin cell, using PPy:PSS with a PSS molecular weight of 1.0 × 106 g/mol, exhibited higher areal capacitance (175.3 mF/cm2), higher volumetric capacitance (584.2 F/cm3), and longer cycling stability (86.3% after 5000 cycles) compared to those of PPy:PSS with PSS molecular weights of 2.0 × 105 and 7.0 × 104 g/mol. This work provides an efficient approach for producing cost-effective and miniaturized supercapacitors with high conductivity and high specific capacitance for practical applications in a variety of electronic devices.
New Pyridinium Type Poly(Ionic Liquids) as Membranes for CO2 Separation

New pyridinium based PILs have been prepared by modification of their precursors based on high molecular weight aromatic polyethers bearing main chain pyridine units. The proposed methodology involves the conversion of the precursors to their ionic analogues via N-methylation reaction, followed by anion exchange methathesis reaction to result in PILs with the desirable anions (tetrafluoroborate and bis(trifluoromethylsulfonyl)imide). These PILs show excellent thermal stability, excellent mechanical properties, and most importantly can form very thin, free standing films with minimum thickness of 3 μm. As expected, the PIL containing the TFSI− anion showed improved CO2 and CH4 permeabilities compared to its analogue containing the BF4−. PIL-IL composites membranes have also been prepared using the same PIL and different percentages of pyridinium based IL where it was shown that the membrane with the highest IL weight percentage (45 wt %) showed the highest CO2 permeability (11.8 Barrer) and a high CO2/CH4 ideal selectivity of 35 at room temperature.
Fire Phenomena of Rigid Polyurethane Foams

Rigid polyurethane foams (RPUFs) typically exhibit low thermal inertia, resulting in short ignition times and rapid flame spread. In this study, the fire phenomena of RPUFs were investigated using a multi-methodological approach to gain detailed insight into the fire behaviour of pentane- and water-blown polyurethane (PUR) as well as pentane-blown polyisocyanurate polyurethane (PIR) foams with densities ranging from 30 to 100 kg/m3. Thermophysical properties were studied using thermogravimetry (TG); flammability and fire behaviour were investigated by means of the limiting oxygen index (LOI) and a cone calorimeter. Temperature development in burning cone calorimeter specimens was monitored with thermocouples inside the foam samples and visual investigation of quenched specimens’ cross sections gave insight into the morphological changes during burning. A comprehensive investigation is presented, illuminating the processes taking place during foam combustion. Cone calorimeter tests revealed that in-depth absorption of radiation is a significant factor in estimating the time to ignition. Cross sections examined with an electron scanning microscope (SEM) revealed a pyrolysis front with an intact foam structure underneath, and temperature measurement inside burning specimens indicated that, as foam density increased, their burning behaviour shifted towards that of solid materials. The superior fire performance of PIR foams was found to be based on the cellular structure, which is retained in the residue to some extent.
Thermoresponsive Microgel Coatings as Versatile Functional Compounds for Novel Cell Manipulation Tools

For the effective use of live cells in biomedicine as in vitro test systems or in biotechnology, non-invasive cell processing and characterisation are key elements. Thermoresponsive polymer coatings have been demonstrated to be highly beneficial for controlling the interaction of adherent cells through their cultivation support. However, the widespread application of these coatings is hampered by limitations in their adaptability to different cell types and because the full range of applications has not yet been fully explored. In the work presented here, we address these issues by focusing on three different aspects. With regard to the first aspect, by using well-defined laminar flow in a microchannel, a highly controllable and reproducible shear force can be applied to adherent cells. Employing this tool, we demonstrate that cells can be non-invasively detached from a support using a defined shear flow. The second aspect relates to the recent development of simple methods for patterning thermoresponsive coatings. Here, we show how such patterned coatings can be used for improving the handling and reliability of a wound-healing assay. Two pattern geometries are tested using mouse fibroblasts and CHO cells. In terms of the third aspect, the adhesiveness of cells depends on the cell type. Standard thermoresponsive coatings are not functional for all types of cells. By coadsorbing charged nanoparticles and thermoresponsive microgels, it is demonstrated that the adhesion and detachment behaviour of cells on such coatings can be modulated.
Chiral MnIII (Salen) Immobilized on Organic Polymer/Inorganic Zirconium Hydrogen Phosphate Functionalized with 3-Aminopropyltrimethoxysilane as an Efficient and Recyclable Catalyst for Enantioselective Epoxidation of Styrene

Organic polymers/inorganic zirconium hydrogen phosphate (ZSPP, ZPS-IPPA, and ZPS-PVPA) functionalized with 3-aminopropyltrimethoxysilane were prepared and used to support chiral MnIII (salen) complexes (Jacobsen’s catalyst). Different characterization methods demonstrated that the chiral MnIII (salen) complexes was successfully supported on the surface of the carrier (ZSPP, ZPS-IPPA, or ZPS-PVPA) through a 3-aminopropyltrimethoxysilane group spacer. The supported catalysts effectively catalyzed epoxidation of styrene with m-chloroperbenzoic acid (m-CPBA) as an oxidant in the presence of N-methylmorpholine N-oxide (NMO) as an axial base. These results (ee%, 53.3–63.9) were significantly better than those achieved under a homogeneous counterpart (ee%, 46.2). Moreover, it is obvious that there was no significant decrease in catalytic activity after the catalyst 3 was recycled four times (cons%: from 95.0 to 92.6; ee%: from 64.7 to 60.1). Further recycles of catalyst 3 resulted in poor conversions, although the enantioselectivity obtained was still higher than that of corresponding homogeneous catalyst even after eight times. After the end of the eighth reaction, the solid catalyst was allowed to stand in 2 mol/L of dilute hydrochloric acid overnight, prompting an unexpected discovery that the catalytic activity of the catalyst was recovered again at the 9th and 10th cycles of the catalyst.
MgCl2-Supported Titanium Ziegler-Natta Catalyst Using Carbon Dioxide-Based Poly(propylene ether carbonate) Diols as Internal Electron Donor for 1-Butene Polymerization

MgCl2-supported titanium Ziegler-Natta catalyst containing CO2-based poly(propylene ether carbonate) diols as a potential internal electron donor (IED) was synthesized and employed for 1-butene polymerization. When compared with the Ziegler-Natta catalyst using poly(polypropylene glycol) as IED, the catalyst prepared with poly(propylene ether carbonate) diols showed good particle morphology, higher activity and stereoselectivity. The results suggested that existence of the carbonate group within the structure of poly(propylene ether carbonate) diols truly plays an important role in improving the performance of the catalyst for the 1-butene polymerization.