Bio-based phytic acid/amino acid complex coating for antimicrobial and flame-retardant cotton fabrics.

Here, a novel multifunctional coating containing bio-based phytic acid (PA), L-glutamic acid (L-Glu), and trimesoyl chloride (TMC) is constructed by a simple soaking strategy, giving cotton fabrics excellent flame retardancy, washability, and antibacterial properties. The coating layer on the cotton surface was prepared via the electrostatic and hydrogen bonding between PA and L-Glu, accompanied by the interface polymerization between PA, L-Glu, and TMC. Among them, the limiting oxygen index value of the treated cotton fabrics (C2 and C2-TMC) was as high as 40 %. During the vertical flammability test, both C2 and C2-TMC cotton showed self-extinguished behavior with a short damaged length (≤50 mm). Remarkably, the LOI of C2-TMC sustained a high value (30 %) even after 300 laundering cycles, maintaining its self-extinguishing behavior in the vertical combustion test. Additionally, in the cone calorimetry test, peak heat release rate and total heat release of treated cotton were lower than control cotton. Surprisingly, after 30 or 60 laundering cycles, the C2-TMC cotton exhibited excellent antibacterial activity against Escherichia coli, Staphylococcus aureus, and Candida albicans due to the continuous exposure of PA and L-Glu. Moreover, the coating layer on the cotton surface had little impact on the mechanical properties and feel of the fabric.

A novel P/N/Si/Zn-containing hybrid flame retardant for enhancing flame retardancy and smoke suppression of epoxy resins.

Currently, additively efficient flame retardants are being developed to enhance the smoke suppression, flame retardancy, and thermal properties of composite materials. To this end, the current study designed and prepared a novel P/N/Si/Zn-containing organic-inorganic hybrid denoted as APHZ. Its inorganic part was 2-methylimidazole zinc salt (ZIF-8), which improved its smoke suppression and catalytic carbonization. The organic part (P/N/Si-containing compound) promoted its flame retardancy and interfacial compatibility between APHZ and epoxy resin (EP). The test results revealed that EP/APHZ-3 composites achieved a V-0 rating and a notable LOI value of 30.7% when introducing 3 wt% APHZ into the EP matrix. Cone calorimetry tests (CCT) further demonstrated that the average heat release rate (av-HRR), total smoke production (TSP), and CO production (COP) of EP/APHZ-3 were reduced by 23.3%, 14.0%, and 21.1%, respectively. Meanwhile, the char residual was increased by 60.6%, as compared to pure EP. Furthermore, the flame-retardant mechanism of EP/APHZ composites was investigated by the XPS, TG-FTIR, and Raman spectroscopy techniques. The observed synergistic effect of the imidazole skeleton ZIF-8 and P/N/Si-containing compound in APHZ facilitated the generation of a dense multi-element char layer, with the condensed phase flame-retardant mechanism playing a dominant role. These findings contribute to developing and designing high-performance flame-retardant EP.

Construction of hierarchical SiO2 microcapsule towards flame retardation, low toxicity and mechanical enhancement of epoxy resins.

A novel approach for improving the flame retardancy, smoke suppression and mechanical properties of epoxy resins (EPs) has been proposed by incorporating functionalized hollow mesoporous silica microcapsules (SHP) loaded with phosphorous silane flame retardants (SCA) and coated with polydopamine (PDA) and transition metals. The proposed approach involves a multi-level structure that combines several mechanisms to enhance the flame-retardant properties of EP. The physical barrier provided by silica serves to impede heat and mass transfer during combustion, while the catalytic carbonization effect of phosphorus and transition metals promotes the formation of a protective char layer, which acts as a barrier to further flame propagation. Incorporating a low loading amount of 3 wt% SHP into the epoxy matrix resulted in EP/SHP-3 composites with significantly improved flame retardancy, as evidenced by a limiting oxygen index of 31.5% and a V-1 rating, in contrast to the values obtained for unmodified EP, which were 23.8% and no rating, respectively. In addition, cone calorimeter test (CCT) results indicated that the total heat release, peak heat release rate and total smoke production of EP/SHP-3 decreased by 18.2%, 25.2% and 18.4%, respectively. Moreover, the improved interfacial compatibility facilitated by polydopamine assists in the dispersion and compatibility of the SHP with the epoxy matrix, leading to better mechanical properties. Herein, the addition of 1 wt% SHP to EP significantly improved its mechanical performance, with a 16.7% increase in tensile strength and a 19.2% increase in impact strength. The design of the multi-level structural approach has the potential to provide new ideas for the simultaneous improvement of fire safety as well as mechanical properties of polymers.

Preparation of Naphthalene-Based Flame Retardant for High Fire Safety and Smoke Suppression of Epoxy Resin.

One of the current challenges in the development of flame retardants is the preparation of an environmentally friendly multi-element synergistic flame retardant to improve the flame retardancy, mechanical performance, and thermal performance of composites. This study synthesized an organic flame retardant (APH) using (3-aminopropyl) triethoxysilane (KH-550), 1,4-phthalaadehyde, 1,5-diaminonaphthalene, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) as raw materials, through the Kabachnik-Fields reaction. Adding APH to epoxy resin (EP) composites could greatly improve their flame retardancy. For instance, UL-94 with 4 wt% APH/EP reached the V-0 rating and had an LOI as high as 31.2%. Additionally, the peak heat release rate (PHRR), average heat release rate (AvHRR), total heat release (THR), and total smoke produced (TSP) of 4% APH/EP were 34.1%, 31.8%, 15.2%, and 38.4% lower than EP, respectively. The addition of APH improved the mechanical performance and thermal performance of the composites. After adding 1% APH, the impact strength increased by 15.0%, which was attributed to the good compatibility between APH and EP. The TG and DSC analyses revealed that the APH/EP composites that incorporated rigid naphthalene ring groups had higher glass transition temperatures (Tg) and a higher amount of char residue (C700). The pyrolysis products of APH/EP were systematically investigated, and the results revealed that flame retardancy of APH was realized by the condensed-phase mechanism. APH has good compatibility with EP, excellent thermal performance, enhanced mechanical performance and rational flame retardancy, and the combustion products of the as-prepared composites complied with the green and environmental protection standards which are also broadly applied in industry.

Design of P-decorated POSS towards flame-retardant, mechanically-strong, tough and transparent epoxy resins.

Epoxy resins (EPs) are known for their durability, strength, and adhesive properties, which make them a versatile and popular material for use in a variety of applications, including chemical anticorrosion, small electronic devices, etc. However, EP is highly flammable due to its chemical nature. In this study, phosphorus-containing organic-inorganic hybrid flame retardant (APOP) was synthesized by introducing 9, 10-dihydro-9-oxa-10­phosphaphenathrene (DOPO) into cage-like octaminopropyl silsesquioxane (OA-POSS) via Schiff base reaction. The improved flame retardancy of EP was achieved by combining the physical barrier of inorganic Si-O-Si with the flame-retardant capability of phosphaphenanthrene. EP composites containing 3 wt% APOP passed the V-1 rating with a value of LOI of 30.1% and showed an apparent reduction in smoke release. Additionally, the combination of the inorganic structure and the flexible aliphatic segment in the hybrid flame retardant provides EP with molecular reinforcement, while the abundance of amino groups facilitates a good interface compatibility and outstanding transparency. Accordingly, EP containing 3 wt% APOP increased in tensile strength, impact strength, and flexural strength by 66.0 %, 78.6 %, and 32.3 %, respectively. The EP/APOP composites had a bending angle lower than 90°, and their successful transition to a tough material highlights the potential of this innovative combination of the inorganic structure and the flexible aliphatic segment. In addition, the relevant flame-retardant mechanism revealed that the APOP promoted the formation of a hybrid char layer containing P/N/Si for EP and produced phosphorus-containing fragments during combustion, showing flame-retardant effects in both condensed and vapor phases. This research offers innovative solutions for reconciling flame retardancy & mechanical performances and strength & toughness for polymers.

Growth of copper organophosphate nanosheets on graphene oxide to improve fire safety and mechanical strength of epoxy resins.

With the high integration of electronic products in our daily life, high-performance epoxy resins (EP) with excellent flame retardancy, smoke suppression, and mechanical strength are highly desired for applications. In this study, copper organophosphate nanosheets were evenly grown on the surface of graphene oxide (GO) via a self-assembly process based on coordination bonding and electrostatic interactions. The resultant nanohybrid endowed EP with satisfactory flame retardant effect and improved mechanical properties. Incorporating functionalized nanosheets of merely 1 wt% loading, the impact strength of the EP nanocomposites improved by 147% when compared to 1% EP-GO. Additionally, the nanosheets inhibited the smoke and heat release of EP, and the limiting oxygen value of EP-EGOPC reached ∼29%. The mechanism analysis verified that the existence of organophosphate and copper-containing components associated with the physical barrier of GO promoted the hybrid aromatization of the char layer, thereby improving the fire safety of epoxy matrix. This research offers a new interfacial method for designing functional nanosheets with good interface compatibility and high flame-retardant efficiency in polymers.

Rational Design of Mesoporous Silica (SBA-15)/PF (Phenolic Resin) Nanocomposites by Tuning the Pore Sizes of Mesoporous Silica.

The development of composite materials with functional additives proved to be an effective way to improve or supplement the required properties of polymers. Herein, mesoporous silica (SBA-15) with different pore sizes were used as functional additives to prepare SBA-15/PF (phenolic resin) nanocomposites, which were prepared by in situ polymerization and then, compression molding. The physical properties and structural parameters of SBA-15 with different pore sizes were characterized by N2 adsorption-desorption, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The thermal properties of the SBA-15/PF hybrid were investigated by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). The mechanical, friction, and dynamic mechanical properties of SBA-15/PF nanocomposites were also studied. The results revealed that the pore sizes of SBA-15 have a significant effect on the resulting SBA-15/PF hybrid and SBA-15/PF nanocomposites. The thermal stability of the SBA-15/PF hybrid was dramatically improved in comparison with pure PF. The friction and dynamic mechanical properties of the SBA-15/PF nanocomposites were enhanced significantly. Specifically, the glass transition temperature (Tg) of the nanocomposite increased by 19.0 °C for the SBA-15/PF nanocomposites modified with SBA-15-3. In addition, the nanocomposite exhibited a more stable friction coefficient and a lower wear rate at a high temperature. The enhancement in thermal and frictional properties for the nanocomposites is ascribed to the confinement of the PF chains or chain segments in the mesopores channels.

Interfacial engineering to construct P-loaded hollow nanohybrids for flame-retardant and high-performance epoxy resins.

Nano flame retardants, as one of the key flame retardants in recent years, have been limited by poor efficiency and weak compatibility. In this study, we propose an interfacial hollow engineering strategy to tackle this problem by assembling P-phytic acid into the hollow cavity of mesoporous SiO2 grafted with a polydopamine transition metal. In this design, the grafted polydopamine-metal coatings on the hybrids can greatly improve their interface compatibility with the polymer matrix, while the loaded phytic acid in the cavity contributes to enhance flame retardancy. Consequently, the resultant hierarchical P-loaded nanohybrids show both high flame retardancy and mechanical reinforcement for the polymer. Taking epoxy resin (EP, a typical thermosetting resin used in large quantities) as a representative, at only 1 wt% loading of the nanohybrids, the impact strength of the nanocomposites improved by 35.7% compared to pure EP. Remarkably, the hybrids can simultaneously endow EP with high flame retardancy (low heat release rate) and satisfactory smoke inhibition. Additionally, the flame-retardant mechanism analysis confirmed that the nanohybrid had a better catalytic carbonization effect on promoting the highly graphitized carbon layer, thereby suppressing the fire hazard of epoxy resins. This research offers a new interfacial hollow engineering method for the construct and design of high-performance EP with nanohybrids.

A resilient and lightweight cellulose/graphene oxide/polymer-derived multifunctional carbon aerogel generated from Pickering emulsion toward a wearable pressure sensor.

In the new era of competitive smart electronics, the development of compressible multifunctional carbon aerogels is highly needed, but still faces enormous challenges. Here we demonstrate a robust strategy to fabricate multifunctional carbon aerogel via freeze-drying of cellulose nanofibers (CNF) and graphene oxide (GO) co-stabilized Pickering emulsion gel followed by high-temperature annealing. The resulting carbon aerogel exhibits tunable mechanical, hydrophilic and hydrophobic properties due to varying the elemental composition and the pyrolysis of introduced polymers. The carbon aerogel is resilient against high compression strain up to 99 % and has ultralow density (1.82 mg/cm3). The CNF/GO/acrylonitrile butadiene styrene-derived carbon aerogel (CRA)-based sensor has shown desirable sensitivity (17.65 kPa-1), ultralow detection limit of pressure (60 Pa), and fast responsive time (130 ms), which is capable of detecting human activity, identifying spatial pressure distribution, and communicating with smartphones via Wi-Fi. Moreover, the carbon aerogel reveals effective thermal insulation and photothermal conversion performance. These results suggest the great potentials for developing lightweight and compressible carbon aerogels with multiple functions to meet various applications.

Cellulose nanofibrils-based hybrid foam generated from Pickering emulsion toward high-performance microwave absorption.

The development of multifunctional microwave absorbers that worked in complex environments remains challenging. In this study, oil-in-water Pickering emulsion gelation approach was combined with freeze-drying to prepare foam-based microwave absorbers along with appealing photo-thermal conversion and thermal insulation. In hybrid foam, cellulose nanofibrils (CNF) and polylactic acid (PLA) serve as three-dimensional skeleton, where carbon nanotubes (CNT) and Fe3O4 nanoparticles are homogeneously incorporated, which forms a conductive network with hetero-interfaces. The optimal reflection loss value of the foam reaches -65.14 dB with a thickness of 3.0 mm. The foam also demonstrate high photo-thermal conversion performance with its surface temperature up to 97 °C after irradiation under 1 Sun for 5 min. Additionally, the foam shows superior thermal insulation comparing with the commercial polyvinyl alcohol and polyurethane foams. This study may offer a promising approach to develop ultralight and high-performance microwave absorber with great potential for multifunctional applications.

Removal of Cr(VI) from Aqueous Solution by Polypyrrole/Hollow Mesoporous Silica Particles.

Abstract: The removal of Cr(VI) in wastewater plays an important role in human health and environment. In this work, polypyrrole/hollow mesoporous silica particle (PPy/HMSNs) adsorbents have been newly synthesized by in-situ polymerization, which prevent the aggregation of pyrrole in the process of polymerization and exhibit highly selective and powerful adsorption ability for Cr(VI). The adsorption process was in good agreement with the quasi-second-order kinetic model and the Langmuir isotherm model. And the maximum adsorption capacity of Cr(VI) was 322 mg/g at 25 °C. Moreover, the removal rate of Cr(VI) by PPy/HMSNs was ~100% in a number of binary systems, such as Cl-/Cr(VI), NO3-/Cr(VI), SO42-/Cr(VI), Zn2+/Cr(VI), Fe3+/Cr(VI), Sn4+/Cr(VI), and Cu2+/Cr(VI). Thus, the PPy/HMSNs adsorbents have great potential for the removal of Cr(VI) in wastewater.

Highly Efficient Removal of Cr(VI) from Aqueous Solutions by Polypyrrole/Monodisperse Latex Spheres.

Pyrrole (Py) is easily agglomerated during the polymerization process, affecting its performance. In this paper, polypyrrole/monodispersed latex sphere (PPy/MLS) composites were prepared using in-situ polymerization for the adsorption of hexavalent chromium (Cr(VI)). The specific surface area of PPy/MLS (39.30 m2/g) was increased relative to that of PPy (24.82 m2/g), thus providing more effective adsorption sites. In addition, the adsorption properties of Cr(VI) under different conditions, including Py content, pH of the aqueous solution, and PPy/MLS dosage, were investigated to reveal the adsorption mechanism. The results showed that PPy/MLS possessed high Cr(VI) adsorption capacities when the Py content was 50 wt %. The maximum adsorption capacity was 343.64 mg/g at pH 2.0 and 25 °C. Remarkably, the adsorbents exhibited an excellent removal rate of Cr(VI) after three cycles of adsorption-desorption (over 99%), suggesting that the adsorbents had exceptional recyclability. Furthermore, the adsorption process followed quasi-second-order kinetics and Langmuir isothermal adsorption model. The high adsorption performance, sustainability, and cost-efficiency make this adsorbent a promising candidate for large-scale Cr(VI) contaminant removal.

Preparation of Polyaniline/Emulsion Microsphere Composite for Efficient Adsorption of Organic Dyes.

Surface-functionalized polymeric microspheres have wide applications in various areas. Herein, monodisperse poly(styrene-methyl methacrylate-acrylic acid) (PSMA) microspheres were prepared via emulsion polymerization. Polyaniline (PANI) was then coated on the PSMA surface via in situ polymerization, and a three-dimensional (3D) structured reticulate PANI/PSMA composite was, thus, obtained. The adsorption performance of the composite for organic dyes under different circumstances and the adsorption mechanism were studied. The obtained PANI/PSMA composite exhibited a high adsorption rate and adsorption capacity, as well as good adsorption selectivity toward methyl orange (MO). The adsorption process followed pseudo-second-order kinetics and the Langmuir isotherm. The maximum adsorption capacity for MO was 147.93 mg/g. After five cycles of adsorption-desorption, the removal rate remained higher than 90%, which indicated that the adsorbent has great recyclability. The adsorbent materials presented herein would be highly valuable for the removal of organic dyes from wastewater.

Transparent and strong polymer nanocomposites generated from Pickering emulsion gels stabilized by cellulose nanofibrils.

We report here the development of transparent and strong polymer composites reinforced by unmodified cellulose nanofibrils (CNFs) with a Pickering emulsion gelation strategy. The CNFs entangle and firmly stabilize on the surface of emulsion droplets containing polymethyl methacrylate (PMMA) solution, leading to the gelation of the emulsions. CNFs/PMMA composites were generated via vacuum filtration and solvent washing of the gel and a subsequent two-step hot pressing. The composites contained a unique self-assembled two-tier hierarchy of CNFs networks and demonstrate promising transparency, tensile strength, flexibility, and an extremely low thermal expansion. Remarkably, these properties are highly tunable with varying the concentration of CNFs and the volume ratio of the water to oil phase. This work offers a facile route to realize the well dispersion of unmodified CNFs in hydrophobic polymer matrix and achieve high performance of polymeric materials reinforced by CNFs.

Crystallization-Induced Red Phosphorescence and Grinding-Induced Blue-Shifted Emission of a Benzobis(1,2,5-thiadiazole)-Thiophene Conjugate.

Mechanochromic luminogens are of significant importance in both academic and technical aspects. Thus far, most mechanochromic compounds exhibit bathochromically shifted emission upon grinding; the examples of those that exhibit blue-shifted emission still remain limited. Herein, a donor-acceptor-donor (D-A-D)-structured conjugate, namely 4,7-di(2-thienyl)-2,1,3-benzothiadiazole (DTBT), comprising benzobis(1,2,5-thiadiazole) and thiophene units, has been carefully synthesized and investigated. DTBT exhibits typical intramolecular charge transfer (ICT) characteristics, crystallization-induced phosphorescence (CIP), and remarkable mechanochromism. Although it merely emits fluorescence in solutions with distinct ICT features, its crystals demonstrate bright-red room-temperature phosphorescence (616 nm) with efficiency up to 25.0% and generate yellow excimer fluorescence (578 nm) upon mechanical grinding, accompanying decreased lifetimes from 10.9 µs to 3.5 ns and a blue-shifted emission of 38 nm. These results highly indicate the feasibility to fabricate novel CIP luminogens with blue-shifted mechanochromism.

Superhydrophobic Melamine Sponge Coated with Striped Polydimethylsiloxane by Thiol-Ene Click Reaction for Efficient Oil/Water Separation.

Superhydrophobic and oleophilic sponges have been demonstrated as promising candidates for oil/water separation. However, there are still challenges in large-scale fabrication of superhydrophobic sponges with low cost and feasible method for industrial applications. Herein, we report a superhydrophobic and oleophilic melamine sponge functionalized by a uniform polydimethylsiloxane (PDMS) film that can be easily coated onto the sponge skeleton through UV-assisted thiol-ene click reactions. The PDMS films are characterized by a hierarchically striped microstructure with an average distance less than 2 µm. Because of the striped microstructure and the hydrophobic property of silicone, a high contact angle of 156.2° was achieved. Importantly, the interconnected open-cell structure of the melamine sponge was preserved by adapting the thickness of the PDMS film. The PDMS-coated melamine sponge exhibited a desirable absorption capacity of 103-179 times its own weight with oils and organic solvents. The excellent mechanical properties of melamine and the flexibility of PDMS enable the PDMS-coated melamine sponges to be squeezed repeatedly without collapsing. This study offers a robust and effective approach in large-scale preparation of a superhydrophobic sponge for large-scale oil spill containment and environmental remediation by the inexpensive commercial polymethylvinylsilicone and facile dip-coating/UV-curing method.

A Highly Sensitive Enzymatic Catalysis System for Trace Detection of Arsenic in Water.

Arsenic (As) is an extremely toxic element that exists in the environment in different chemical forms. The detection of arsenic in potable water remains a challenging task. This study presents a highly sensitive enzymatic catalysis system for trace sensing of inorganic arsenic in water. This is the first enzyme-catalyzed fluorescence assay capable of detecting arsenic at concentrations below the allowable level adopted by the World Health Organization (10 ppb in drinking water). The enzyme catalytically produces fluorescent NADH in the presence of arsenate, which enables facile detection of arsenate at concentrations in the 0-200 ppb range. Calibration curves made at a set time interval allow accurate determination of unknown arsenic samples. This method holds potential for interfacing with automated analytical sampling systems to allow arsenic determinations in environmental health applications.