RESUMO
Organic polymer materials, as the most abundantly produced materials, possess a flammable nature, making them potential hazards to human casualties and property losses. Target polymer design is still hindered due to the lack of a scientific foundation. Herein, we present a robust, generalizable, yet intelligent polymer discovery framework, which synergizes diverse capabilities, including the in situ burning analyzer, virtual reaction generator, and material genomic model, to achieve results that surpass the sum of individual parts. Notably, the high-throughput analyzer created for the first time, grounded in multiple spectroscopic principles, enables in situ capturing of massive combustion intermediates; then, the created realistic apparatus transforming to the virtual reaction generator acquires exponentially more intermediate information; further, the proposed feature engineering tool, which embedded both polymer hierarchical structures and massive intermediate data, develops the generalizable genomic model with excellent universality (adapting over 20 kinds of polymers) and high accuracy (88.8%), succeeding discovering series of novel polymers. This emerging approach addresses the target polymer design for flame-retardant application and underscores a pivotal role in accelerating polymeric materials discovery.
RESUMO
Flexible polyurethane foam (FPUF) is a ubiquitous material utilized in furniture cushions, mattresses, and various technical applications. Despite the widespread use, FPUF faces challenges in maintaining long-lasting flame retardancy and aging resistance, particularly in harsh environments, while retaining mechanical robustness. Here, we present a novel approach to address these issues by enhancing FPUF through multiple free-radical-trapping and hydrogen-bonding mechanisms. A hindered amine phosphorus-containing polyol (DTAP) was designed and chemically introduced into FPUF. The distinctive synergy between hindered amine and phosphorus-containing structures enables the formation of multiple hydrogen bonds with urethane, while also effectively capturing free radicals across a broad temperature spectrum. As a result, incorporating only 5.1 wt% of DTAP led to the material successfully passing vertical burning tests and witnessing notable enhancements in tensile strength, elongation at break, and tear strength. Even after enduring accelerated thermal aging for 168 hours, the foam maintained exceptional flame retardancy and mechanical properties. This study offers novel insights into material enhancement, simultaneously achieving outstanding long-lasting flame retardancy, toughness, and anti-aging performance.
RESUMO
Passive radiant cooling is a potentially sustainable thermal management strategy amid escalating global climate change. However, petrochemical-derived cooling materials often face efficiency challenges owing to the absorption of sunlight. We present an intrinsic photoluminescent biomass aerogel, which has a visible light reflectance exceeding 100%, that yields a large cooling effect. We discovered that DNA and gelatin aggregation into an ordered layered aerogel achieves a solar-weighted reflectance of 104.0% in visible light regions through fluorescence and phosphorescence. The cooling effect can reduce ambient temperatures by 16.0°C under high solar irradiance. In addition, the aerogel, efficiently produced at scale through water-welding, displays high reparability, recyclability, and biodegradability, completing an environmentally conscious life cycle. This biomass photoluminescence material is another tool for designing next-generation sustainable cooling materials.
RESUMO
Dynamic covalent chemistry is a promising strategy for developing recyclable thermosets and their carbon fiber reinforced composites, in line with the goal of green and sustainable development. However, a significant challenge lies in balancing the dynamic reversibility and the desired service performances, such as thermal, mechanical properties, and flame retardancy. It has hindered the broader application of dynamic materials beyond the initial proof of concept. This concept provides an overview of the current state of research on phosphorus-containing covalent adaptable networks (CANs), highlighting key designing and regulating principles for tailoring comprehensive properties including flame retardancy, mechanical and thermal properties, as well as dynamic behaviours such as malleability, reprocessability and degradability. Finally, new frontiers and opportunities in developing high-performance sustainable CANs-based thermosets and their carbon fiber composites for structural engineering applications are prospected.
RESUMO
Polyurethane (PU) foams, pivotal in modern life, face challenges suh as fire hazards and environmental waste burdens. The current reliance of PU on potentially ecotoxic halogen-/phosphorus-based flame retardants impedes large-scale material recycling. Here, our demonstrated controllable catalytic cracking strategy, using cesium salts, enables self-evolving recycling of flame-retardant PU. The incorporation of cesium citrates facilitates efficient urethane bond cleavage at low temperatures (160 °C), promoting effective recycling, while encouraging pyrolytic rearrangement of isocyanates into char at high temperatures (300 °C) for enhanced PU fire safety. Even in the absence of halogen/phosphorus components, this foam exhibits a substantial increase in ignition time (+258.8%) and a significant reduction in total smoke release (-79%). This flame-retardant foam can be easily recycled into high-quality polyol under mild conditions, 60 °C lower than that for the pure foam. Notably, the trace amounts of cesium gathered in recycled polyols stimulate the regenerated PU to undergo self-evolution, improving both flame-retardancy and mechanical properties. Our controllable catalytic cracking strategy paves the way for the self-evolutionary recycling of high-performance firefighting materials.
RESUMO
Upgrading thermosetting polymer waste and harvesting unwanted electromagnetic energy are of great significance in solving environmental pollution and energy shortage problems. Herein, inspired by the glass-blowing art, a spontaneous, controllable, and scalable strategy is proposed to prepare hollow carbon materials by inner blowing and outside blocking. Specifically, hierarchically neuron-like hollow carbon materials (HCMSs) with various sizes are fabricated from melamine-formaldehyde sponge (MS) waste. Benefiting from the synergistic of the hollow "cell body" and the connected "protrusions" networks, HCMSs reveal superior electromagnetic absorption performance with a strong reflection loss of -54.9 dB, electromagnetic-heat conversion ability with a high conversion efficiency of 34.4%, and efficient energy storage performance in supercapacitor. Furthermore, a multifunctional device integrating electromagnetic-heat-electrical energy conversion is designed, and its feasibility is proved by experiments and theoretical calculations. The integrated device reveals an output voltage of 34.5 mV and a maximum output power of 0.89 µW with electromagnetic radiation for 60 s. This work provides a novel solution to recycle polymer waste, electromagnetic energy, and unwanted thermal energy.
RESUMO
Plastics serve as an essential foundation in contemporary society. Nevertheless, meeting the rigorous performance demands in advanced applications and addressing their end-of-life disposal are two critical challenges that persist. Here, an innovative and facile method is introduced for the design and scalable production of polycarbonate, a key engineering plastic, simultaneously achieving high performance and closed-loop chemical recyclability. The bisphenol framework of polycarbonate is strategically adjusted from the low-bond-dissociation-energy bisphenol A to high-bond-dissociation-energy 4,4'-dihydroxydiphenyl, in combination with the incorporation of polysiloxane segments. As expected, the enhanced bond dissociation energy endows the polycarbonate with an extremely high glow-wire flammability index surpassing 1025 °C, a 0.8 mm UL-94 V-0 rating, a high LOI value of 39.2%, and more than 50% reduction of heat and smoke release. Furthermore, the π-π stacking interactions within biphenyl structures resulted in a significant enhancement of mechanical strength by as more as 37.7%, and also played a positive role in achieving a lower dielectric constant. Significantly, the copolymer exhibited outstanding closed-loop chemical recyclability, allowing for facile depolymerization into bisphenol monomers and the repolymerized copolymer retains its high heat and fire resistance. This work provides a novel insight in the design of high-performance and closed-loop chemical recyclable polymeric materials.
RESUMO
Recycling strategies for mixed plastics and textile blends currently aim for recycling only one of the components. Here, we demonstrate a water coupling strategy to co-hydrolyze polyester/cotton textile blends into polymer monomers and platform chemicals in gamma-valerolactone. The blends display a proclivity for achieving an augmented 5-hydroxymethylfurfural yield relative to the degradation of cotton alone. Controlled experiments and preliminary mechanistic studies underscore that the primary driver behind this heightened conversion rate lies in the internal water circulation. The swelling and dissolving effect of gamma-valerolactone on polyester enables a fast hydrolysis of polyester at much lower concentration of acid than the one in the traditional hydrolysis methods, effectively mitigating the excessive degradation of cotton-derived product and undesirable product formation. In addition, the system is also applicable to different kinds of blends and PET mixed plastics. This strategy develops an attractive path for managing end-of-life textiles in a sustainable and efficient way.
RESUMO
Biodegradable polymers with shape memory effects (SMEs) offer promising solutions for short-term medical interventions, facilitating minimally invasive procedures and subsequent degradation without requiring secondary surgeries. However, achieving a good balance among desirable SMEs, mechanical performance, degradation rate, and bioactivities remains a significant challenge. To address this issue, we established a strategy to develop a versatile biodegradable polyurethane (PPDO-PLC) with tunable hierarchical structures via precise chain segment control. Initial copolymerization of l-lactide and ε-caprolactone sets a tunable Tg close to body temperature, followed by block copolymerization with poly(p-dioxanone) to form a hard domain. This yields a uniform microphase-separation morphology, ensuring robust SME and facilitating the development of roughly porous surface structures in alkaline environments. Cell experiments indicate that these rough surfaces significantly enhance cellular activities, such as adhesion, proliferation, and osteogenic differentiation. Our approach provides a methodology for balancing biodegradability, SMEs, three-dimensional (3D) printability, and bioactivity in materials through hierarchical structure regulation.
Assuntos
Poliuretanos , Poliuretanos/química , Poliuretanos/farmacologia , Proliferação de Células/efeitos dos fármacos , Materiais Biocompatíveis/química , Materiais Biocompatíveis/farmacologia , Animais , Porosidade , Adesão Celular/efeitos dos fármacos , Osteogênese/efeitos dos fármacos , Camundongos , Poliésteres/química , Diferenciação Celular/efeitos dos fármacos , Lactonas/química , Lactonas/farmacologia , Humanos , Caproatos/química , Dioxanos/química , PolímerosRESUMO
Plastic pollution is an emerging global threat due to lack of effective methods for transforming waste plastics into useful resources. Here, we demonstrate a direct oxidative upcycling of polyethylene into high-value and high-volume saturated dicarboxylic acids in high carbon yield of 85.9 % in which the carbon yield of long chain dicarboxylic (C10-C20) acids can reach 58.9% over cobalt-doped MCM-41 molecular sieves, in the absence of any solvent or precious metal catalyst. The distribution of the dicarboxylic acids can be controllably adjusted from short-chain (C4-C10) to long-chain ones (C10-C20) through changing cobalt loading of MCM-41 under nanoconfinement. Highly and sparsely dispersed cobalt along with confined space of mesoporous structure enables complete degradation of polyethylene and high selectivity of dicarboxylic acid in mild condition. So far, this is the first report on highly selective one-step preparation of long chain dicarboxylic acids. The approach provides an attractive solution to tackle plastic pollution and a promising alternative route to long chain diacids.
RESUMO
The inherent flammability of most polymeric materials poses a significant fire hazard, leading to substantial property damage and loss of life. A universal flame-retardant protective coating is considered as a promising strategy to mitigate such risks; however, simultaneously achieving high transparency of the coatings remains a great challenge. Here, inspired by the moth eye effect, we designed a nanoporous structure into a protective coating that leverages a hydrophilic-hydrophobic interactive assembly facilitated by phosphoric acid protonated amino siloxane. The coating demonstrates robust adhesion to a diverse range of substrates, including but not limited to fabrics, foams, paper, and wood. As expected, its moth-eye-inspired nanoporous structure conferred a high visible light transparency of >97% and water vapor transmittance of 96%. The synergistic effect among phosphorus (P), nitrogen (N), and silicon (Si) largely enhanced the char-forming ability and restricted the decomposition of the coated substrates, which successfully endowed the coating with high fire-fighting performance. More importantly, for both flexible and rigid substrates, the coated samples all possessed great mechanical properties. This work provides a new insight for the design of protective coatings, particularly focusing on achieving high transparency.
RESUMO
Although many approaches have been proposed to recycling waste epoxy resin (EP), the separation of mixed degraded products remains a challenge due to their similar structures. To address this, we present a catalytic oxidation strategy that enables mild degradation of EP and in situ separation of degraded products through supramolecular interactions. The oxidative degradation relies on FeIV=O radicals with strong oxidizing properties, which are generated from the electron transfer of FeCl2 with reaction reagents. As the FeIV=O radicals attacked the C-N bonds of EP, EP was broken into fragments rich in active functional groups. Meanwhile, the FeIV=O radicals were reduced to iron ions that can coordinate with the carboxyl groups on the fragments. As a result, the degraded products with different carboxyl content can be effortlessly separated into liquid and solid phase by coordinating with the catalyst. The success of this work lays the foundation for high-value application of degraded products and provides new design ideas for recycling waste plastics with complex compositions.
RESUMO
Persistent organic pollutants (POPs) sourced by the forest fire release are emerging as significant contributors. Despite their increasing importance, the impact of forest fires on POPs remains inadequately explored and an unclear understanding. Herein, the research, choosing four typical forest combustibles, focuses on the relationship between typical POPs and wildfire parameters by assessing the predominant compounds and their concentration in POPs emissions from such fuels through molecular-level analysis. Experiments reveal forest combustibles thermally degrade to release products, releasing a variety of products, including acids (>7.94 %), aldehydes (>2.32 %), ketones (>3.40 %), alcohols (>7.70 %), esters (>2.33 %), ethers (>4.44 %), hydrocarbons (>6.36 %), aromatic compounds (>21.40 %), and nitrogen-bearing compounds (>11.83 %); notably, aromatic compounds, containing substantial concentrations, are also recognized as POPs. By delving into the pyrolysis (20 °C·ms-1) and burning processes (25, 35 and 50 kW/m2) of forest combustibles, we can gain a comprehensive understanding of the origin of POPs in wildfires. Moreover, Pearson correlation analysis is employed to establish connections between emitting volatiles and forest fire risk, further unveiling a significant correlation between fire hazards of forest combustibles and the presence of aromatic compounds (Correlation over 0.8). These findings are crucial for comprehending the POPs in forests and evaluating forest fire hazards at the molecular level.
RESUMO
Polymeric materials, rich in carbon, hydrogen, and oxygen elements, present substantial fire hazards to both human life and property due to their intrinsic flammability. Overcoming this challenge in the absence of any flame-retardant elements is a daunting task. Herein, we introduce an innovative strategy employing catalytic polymer auto-pyrolysis before combustion to proactively release CO2, akin to possessing responsive CO2 fire extinguishing mechanisms. We demonstrate that potassium salts with strong nucleophilicity (such as potassium formate/malate) can transform conventional polyurethane foam into materials with fire safety through rearrangement. This transformation results in the rapid generation of a substantial volume of CO2, occurring before the onset of intense decomposition, effectively extinguishing fires. The inclusion of just 1.05 wt% potassium formate can significantly raise the limiting oxygen index of polyurethane foam to 26.5%, increase the time to ignition by 927%, and tremendously reduce smoke toxicity by 95%. The successful application of various potassium salts, combined with a comprehensive examination of the underlying mechanisms, underscores the viability of this strategy. This pioneering catalytic approach paves the way for the efficient and eco-friendly development of polymeric materials with fire safety.
RESUMO
Polyolefin separators are the most commonly used separators for lithium batteries; however, they tend to shrink when heated, and their Li+ transference number (t Li +) is low. Metal-organic frameworks (MOFs) are expected to solve the above problems due to their high thermal stability, abundant pore structure, and open metal sites. However, it is difficult to prepare high-porosity MOF-based membranes by conventional membrane preparation methods. In this study, a high-porosity free-standing MOF-based safety separator, denoted the BCM separator, is prepared through a nano-interfacial supramolecular adhesion strategy. The BCM separator has a large specific surface area (450.22 m2 g-1) and porosity (62.0%), a high electrolyte uptake (475 wt%), and can maintain its morphology at 200 °C. The ionic conductivity and t Li + of the BCM separator are 1.97 and 0.72 mS cm-1, respectively. Li//LiFePO4 cells with BCM separators have a capacity retention rate of 95.07% after 1100 cycles at 5 C, a stable high-temperature cycling performance of 300 cycles at 80 °C, and good capacity retention at -40 °C. Li//NCM811 cells with BCM separators exhibit significantly improved rate performance and cycling performance. Pouch cells with BCM separators can work at 120 °C and have good safety at high temperature.
RESUMO
Flame retardants containing biomass receive growing interest in environmental friendliness and sustainability but usually face the low flame-retardant efficiency and deterioration on mechanical property of matrix. Herein, a calcium gluconate-based flame retardant (CG@APP) was chemically prepared using calcium gluconate (CG) and ammonium polyphosphate (APP) via ion exchange reaction, and enabled the excellent fire safety and mechanical enhancement for epoxy resin (EP). The resulted EP composites containing 6 wt% CG@APP (EP/CG@APP6) exhibited V-0 ratings in UL-94 test. Furthermore, with respect to EP/APP6, the peak of heat release rate (pHRR) and peak of smoke production rate (pSPR) of EP/CG@APP6 decreased by 70.5 % and 50.0 %, respectively. The well synergistic flame-retardant mechanism of CG@APP between gaseous and solid phases was revealed to generate denser and more continuous charring residuals, which could do well work on insulation for heat transfer and fuel diffusion. In addition, the shell rich in hydroxyl group and Ca2+ on the surface of CG@APP well enhanced the interface compatibility through the hydrogen bond and coordinated bond, thus the tensile strength, flexural strength and impact strength of EP/CG@APP6 increased by 18.2 %, 4.5 % and 9.1 % compared with pure EP, respectively. This work provided a simple and sustainable way to construct excellent fire-safety composites.
Assuntos
Resinas Epóxi , Retardadores de Chama , Gluconato de Cálcio , Biomassa , Difusão , PolifosfatosRESUMO
Liquid crystal actuators conventionally undergo shape changes across an order-disorder phase transition between liquid crystal (LC) and isotropic phases. In this study, we introduce an innovative Liquid Crystal Polymer (LCP) actuator harnessing an order-order LC phase transition mechanism. The LCP film is easily stretchable within the LC phase, facilitated by the π-π stacking of phenyl groups serving as robust physical crosslinking points, and thereby transforms to a stable monodomain structure. The resultant monodomain LCP actuator shows a distinctive reversible dynamic shape change, exhibiting extension followed by contraction along the LC director on cooling. The extension is propelled by the reversible smectic C to smectic A phase transition, and the contraction is attributed to the re-entry to the smectic C phase from smectic A phase. Thermal annealing temperature determines this peculiar dynamic shape change, which occurs during both heating and cooling processes. This pivotal attribute finds manifestation in gripper and flower-shaped actuators, adeptly executing grabbing and releasing as well as blooming and closure motions within a single thermal stimulation. In essence, our study introduces an innovative approach to the realm of LCP actuators, ushering in a new avenue for the design and fabrication of versatile and dynamically responsive LCP actuators.
RESUMO
More single-use plastics are accumulating in the environment, and likewise biodegradable plastics (BPs), which are being vigorously promoted, cannot escape the fate. Currently, studies on the actual degradation of BPs in open-air and freshwaters are underrepresented despite they are potentially headmost leakage and contamination sites for disposable BPs. Herein, we compared the degradation behavior of six BP materials and non-degradable polypropylene (PP) plastics over a 1-year in situ suspension in the high-humidity air, a eutrophic river, and an oligotrophic lake. Moreover, a 3-months laboratory incubation was performed to detect the release of dissolved organic carbon (DOC) from BPs. In both air and freshwaters, poly(p-dioxanone) (PPDO) degraded significantly while PP and polylactic acid (PLA) showed no signs of degradation. The average degradation rates of three poly(butylene adipate-co-terephthalate) (PBAT)-based films varied: 100% in river, 55% in lake, and 10% in air. In addition to PLA, surface chemical groups, hydrophilicity, and thermal stability of BPs changed, and microplastics were found on their surfaces. Correspondingly, BPs with faster degradation rates released relatively higher amounts of DOC. Environmental microbial and chemical characteristics may contribute to differences in BP degradation besides polymer specificity. Altogether, our results indicate the need for appropriate monitoring of BPs.
RESUMO
Thermosetting polyimide (PI) has attracted extensive attention for its excellent properties, but the approaches to its end-of-life management are not sustainable, posing great threat to the ecosystem. Herein, this work proposes a mild, sustainable, and full recovery path for recycling waste carbon fiber reinforced phenylethynyl end-capped PI resin composites. In addition to recycling reaction reagent and woven carbon fiber, degraded products (DPETI) can be fully and directly used as high-performance and sustainable adhesives. DPETI exhibits strong adhesion to various surfaces, with a maximum adhesion strength of 1.84 MPa. Due to the strong supramolecular polymerization behavior without solvent dependence, DPETI demonstrates higher adhesive strength of 2.22 MPa in the extreme environment (-196 °C), which is maintained even after 10 cycles. This work sparks a new thinking for plastic wastes recycling that is to convert unrecyclable wastes into new and sustainable materials, which has the potential to establish new links within circular economies and influence the development of materials science.
RESUMO
Smart and dynamic electromagnetic interference (EMI) shielding materials possess a remarkable capacity to modify their EMI shielding abilities, rendering them invaluable in various civil and military applications. However, the present response mechanism of switch-type EMI shielding materials is slightly restricted, as it primarily depends on continuous pressure induction, thereby resulting in concerns regarding their durability and reliability. Herein, for the first time, we demonstrate a novel method for achieving solvent-responsive, reversible switching, and robust EMI shielding capabilities using a controlled proton-reservoir ordered gel. The gel contains polyaniline (PANI) and sodium alginate (SA). Initially, SA acts as a proton reservoir for PANI in an aqueous system, enhancing the doping level of PANI and improving its electrical conductivity. Additionally, PANI and SA chains respond to diverse polar solvents, such as water, acetonitrile, ethanol, n-hexane, and air, inducing distinct conformations that affect the degree of PANI conjugation and electron migration along the chains. This process is reversible and non-destructive to the polymer chain, ensuring the effective and uncompromised performance of the EMI shielding switch. We can achieve precise and reversible tuning (on/off) of EMI shielding with different effectiveness levels by manipulating the solvents within the framework. This work opens a new solvent-stimuli avenue for the development of EMI shielding materials with reliable and intelligent on/off switching capabilities.