Acrylic Acid Research Articles

Preparation of rosin epoxy soybean oil acrylate with high bio-renewable carbon content for 3D printing

A kind of rosin epoxy soybean oil acrylate (RBAESO) containing high bio-renewable carbon content was synthesized by using rosin and acrylic acid (AA) to react with epoxidized soybean oil (ESO), and the effects of rosin addition amount on the properties of RBAESO resin and its cured film were investigated. The reaction activity between carboxylic acid and the epoxy group was found improved by introducing natural rosin to replace part of AA and increasing the C=C double bond density of the molecular structure. The best prepolymer resin RBAESO-15% performance was obtained with a reaction molar ratio of ESO: AA: Rosin = 1.05:0.85: 0.15. RBAESO-15% has a viscosity of 16500 mPa·s. The cured film of RBAESO-15% displayed high pencil hardness up to H, and 2mm of flexibility. The introduction of rosin also increased the high bio-renewable carbon content of the resin from 80.3% to 89.6% compared to epoxy soybean oil acrylate (AESO). UV cured tested show the C=C double-bond conversion of RBAESO-15% is about 86.4%, which is higher than that of AESO, and the tensile strength and elongation at break increased from 3.2MPa and 7.4% to 14.4MPa and 12.1%, respectively. This indicates that RBAESO displays better coating film performance than those of AESO. In addition, RBAESO-15% with 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO) can be applied to the laser cladding deposition (LCD) 3D printers.

Effect of Production Scale on the Techno-economic Viability and Environmental Life Cycle Analysis of Lactic Acid Production in a Sugarcane Biorefinery

Biorefineries are vital for advancing circular economy and reducing the effects of products fossil fuels derived products on the environment. However, biorefineries often operate at smaller production scales than fossil refineries due to limited feedstock availability, which may be addressed by centralised processing with multiple feedstock sources. Lactic acid (LA) has several industrial applications and is a platform chemical used to produce products like acrylic acid and propylene glycol. The economic and environmental performances of an integrated biorefinery at different production scales, through different levels of feedstock centralization, were investigated, to determine the optimal scale for sugarcane-based LA production. Decreasing values for the minimum selling price (MSP; 1,312 to 849 US$.t-1) and increasing internal rates of return (IRRs; 31 to 64%) were observed with increasing conversion scales of sugarcane A-molasses. The MSPs decrease from 90-450 ktLA.y-1 with small improvements in profitability beyond 450 ktLA.y-1, as confirmed by stochastic financial uncertainty analysis. In the environmental assessment, a linear increase was observed across all impact categories, mainly due to the added fuel consumption for feedstock transportation. LA production had a GWP100 range of 0.87-0.95kg CO2-eq.kgLA-1 and an abiotic depletion potential of 12-13 MJ.kgLA-1 which increased as the scale increased. In the ozone depletion category emissions of 9.96×10-8-1.13×10-7kg CFC-11 eq.kgLA-1 comparable to other studies available in literature. Similarly, emission ranges of 1.11-1.17, 0.63-0.66, and 1,581-1,641kg 1,4-DB eq.kgLA-1 were obtained in the human toxicity, freshwater and marine aquatic ecotoxicity categories as the scale increased. Environmentally the smallest scale at which transportation of feedstock was avoided (i.e. 90 ktLA.y-1) is preferred as opposed to 450 ktLA.y-1 for economic performance.

Preparation of thickened P(AA-AMPS) copolymers by inverse emulsion polymerization and evaluation of fracturing and oil flooding performance

Polymer is an essential type of fracturing fluid. Nevertheless, issues such as slow dissolution, high initial viscosity, and challenges in storage, transportation and operation limit its application. To address these issues, a thickened copolymer P(AA-AMPS) was synthesized by inverse emulsion polymerization using acrylic acid (AA) and 2-acrylamide-2-methylpropanesulfonic acid (AMPS) as the monomers. Three P(AA-AMPS) copolymers were obtained by changing the weight ratio of AA and AMPS monomers. When the weight ratio of AA to AMPS monomers was 8.2:1.8, the P(AA-AMPS) copolymer solution exhibited the best interfacial activity, reducing the oil–water interfacial tension to 3.95 mN m−1. The initial viscosity of the copolymer was only 66 mPa s, but its solution could reach a high viscosity of up to 817 mPa s. P(AA-AMPS) copolymers demonstrated good resistance for temperature and shear. For instance, the viscosity of copolymer solution still remained 300 mPa s with a shear rate of 170 s−1 at 90 °C. Furthermore, P(AA-AMPS) copolymers had excellent gel-breaking capacity, sand suspension stability, wettability and oil displacement ability. Therefore, the integration of fracturing and oil flooding can be realized for the development of low permeability reservoirs by selecting appropriate copolymers. P(AA-AMPS) copolymers would play an important role due to their significant viscosity differences and easy operation on storage, transportation and application.

Three-dimensionally assembled polyelectrolyte multilayers-functionalized silica nanowire membrane for highly-efficient adsorptive separation of copper ions from water

High-performance materials for heavy metal ion removal are highly demanded in environmental treatment. Membrane adsorption has the advantages of being easy to operate and avoiding secondary pollution. It remains challenging to prepare adsorption membranes with both high removal rate and high permeability. Here, we present a novel strategy for preparing poly(acrylic acid) (PAA) and polyethyleneimine (PEI) multilayer-assembled silica nanowires (SiO2 NWs) membrane with abundant, multiple functional groups on a highly porous network for Cu(II) capture. The SiO2 NWs in the hybrid membranes serve as a rigid 3D framework to improve membrane porosity and water flux, while the polyelectrolyte multilayers assembled on the SiO2 NWs provide abundant, highly accessible adsorption sites for Cu(II) uptake. The adsorption capacity of the membranes can be tuned by changing the dosage of the assembled SiO2 NWs and the PAA/PEI pair layers. The maximum adsorption capacity of the active polyelectrolyte layer for SiO2 NWs@(PAA/PEI)4 composite membrane was 272.5 mg/g toward Cu(II), outperforming the counterpart (PAA/PEI)4 membrane (97.5 mg/g) after removal of the SiO2 NWs framework. The hybrid membrane shows excellent adsorption performance for the removal of low concentrations of Cu(II) in a dynamic adsorption mode, and the removal rate is maintained at above 90% after eight recycles.

Rapid preparation of bioadhesive hydrogels containing catechol moieties at room temperature with reproducible adhesion to wet tissues, antimicrobial, antioxidant capacity for noncompressive hemostasis.

In order to cope with the massive tissue bleeding caused by sudden trauma and the demand for bioengineering materials with adjustable wet adhesion properties, this study formed the first layer of network by adding galactomannan (GG) and collagen (Col) structure, and then use the Fe3+-urushiol (UH) redox system to activate free radicals to initiate the polymerization of acrylic acid (AA) to quickly form an interpenetrating double network hydrogel. The cis hydroxyl group in GG and the hydroxyl group of UH form dynamic covalent borate ester bonds with borate ions in the borax solution, and use their responsiveness to pH to control the catechol group to achieve controllable adhesion. UH and Fe3+ endowed the hydrogel with excellent antibacterial ability, while adding Col enhanced the mechanical properties of the hydrogel. The elastic modulus and toughness increased from 4.32 kPa and 92.9 kJ/m3 to 18.90 kPa and 264.54 kJ/m3. In addition, due to the joint action of UH and Col, the hydrogel dressing can achieve rapid hemostasis within 20 s. In short, this hydrogel dressing has good biocompatibility, inherent antibacterial ability, adjustable moist tissue adhesion properties and rapid hemostatic ability, and is expected to become a candidate for wound hemostasis dressing.

Lignin-coated liquid metals-induced synthesis of deep eutectic solvent-based hydrogels with environmentally tolerant for strain sensors

In the work, alkali lignin (AL) was used as a coating layer for dispersing liquid metals (LM) in a ternary DES (choline chloride/ethylene glycol/water) system and generating free radical-catalyzed acrylic acid (AA) polymerization. The preparation of flexible sensors had high electrical conductivity (0.33 S·m-1), excellent self-healing and mechanical properties (84.7 KPa). The presence of AL facilitated the dispersion of LM in the DES system and the formation of a flexible hydrogel without the addition of an initiator. Moreover, DES was used as the liquid component of the PAA-AL2@LM2 hydrogel made it more environmentally tolerant and had better water retention. Even at -20 °C, the hydrogel exhibited low electrical resistance (131.4 Ω). The moisture loss of the prepared hydrogel was only 9% after 7 days at room temperature. This work exploited the significant advantages of DES and lignin-based materials in dispersing LM to provide a new technique for the preparation of metal-polymer composite hydrogels, which has great potential in the field of flexible sensors.

Ultrasound-assisted synthesis of methyl acrylate using Amberlyst-15 catalyst: optimization using response surface method

Ultrasound-assisted synthesis of methyl acrylate was performed in a solvent-free ultrasound batch reactor using acid ion exchange resin (amberlyst-15) as a heterogeneous catalyst. Influence of different reaction parameters such as temperature (40-70°C), alcohol to acid mole ratio (2-8), catalyst loading (0-10 % w/w), and addition of molecular sieves (0-8%), ultrasound power (0-120W), and duty cycle (20-80%) on the activity of reaction were investigated through one parameter at a time. Further, four significant parameters were optimized using response surface methodology using a central composite design. The maximum conversion of acrylic acid 61.02 %, was obtained at optimum reaction conditions at 61°C reaction temperature, 6.5 alcohol to acid mole ratio, 7.85% catalyst loading, and 60% ultrasound duty cycle. The equilibrium conversion improved from 29.2% to 61.02%, with a significant decrease in reaction time as compared to the conventional approach.

Poly acrylic acid patterning by electron beam lithography

Poly acrylic acid (PAA) is a polymer and a derivative of acrylic acid that is a superabsorbent, being able to absorb and retain water, and swell many times beyond its original volume. This property classifies it into a group of polymers called hydrogels. Hydrogels are being investigated in emerging applications such as drug delivery, biosensors, tissue engineering, wound healing bandages, and more. The ability to lithographically pattern hydrogel materials to specific dimensions at the micro and nanoscales can be very useful in devices and sensors. Limited work has been done on characterizing PAA for lithographic purposes, and so, this work investigates the ability to pattern PAA by electron beam lithography (EBL). PAA is interesting in that its carrier solvent, developer, and remover are all water alone, which may make it attractive for processes or materials that cannot tolerate solvents, acids, and bases used with other common EBL resists. PAA behaves as a negative tone resist with a relatively low base dose of 75 μC/cm2 at 100 kV acceleration voltage. The resolution is limited to 1.8 μm due to a low contrast of 1.29. However, PAA may still have many uses at that resolution where the positioning and dimension control of a hydrogel could be useful. Furthermore, PAA can successfully be used for pattern transfer with either a metal liftoff process or a silicon plasma etch.

Development of an Ionic Conductive Elastomer from the Photocopolymerization of a Ternary Polymerizable Deep Eutectic Solvent for Human Motions Sensing.

Polymerizable deep eutectic solvents (PDES) represent a novel class of ionic liquids characterized by the presence of polymerizable groups in their hydrogen-bond donor or acceptor components. Within the realm of flexible electronics, PDES is emerged as a promising material for the fabrication of sensors that exhibit both flexibility and stretchability. This research employs the UV-initiated photocopolymerization of a ternary PDES composed of choline chloride (ChCl), 2-hydroxyethyl acrylate (HEA), and itaconic acid (IA), to synthesize an ionic conductive elastomer (ICE) that boasts desirable comprehensive performances, which can be controlled by meticulously adjusting the ratios of these components. The fabrication process is streamlined and efficient, utilizing cost-effective and eco-friendly materials. This elastomer exhibits favorable ionic conductivity (1.70 × 10-2-5.45 × 10-2 S m-1), mechanical strength (0.48-1.21MPa stress at break, 395-701% elongation at break), adhesion capacity (49-120kPa adhesion strength), and sensing sensitivity toward human motions.

Acidic polymers reversibly deactivate phages due to pH changes.

Bacteriophages are promising as therapeutics and biotechnological tools, but they also present a problem for routine and commercial bacterial cultures, where contamination must be avoided. Poly(carboxylic acids) have been reported to inhibit phages' ability to infect their bacterial hosts and hence offer an exciting route to discover additives to prevent infection. Their mechanism and limitations have not been explored. Here, we report the role of pH in inactivating phages to determine if the polymers are unique or simply acidic. It is shown that lower pH (=3) triggered by either acidic polymers or similar changes in pH using HCl lead to inhibition. There is no inhibitory activity at higher pHs (in growth media). This was shown across a panel of phages and different molecular weights of commercial and controlled-radical polymerization-derived poly(acrylic acid)s. It is shown that poly(acrylic acid) leads to reversible deactivation of phage, but when the pH is adjusted using HCl alone the phage is irreversibly deactivated. Further experiments using metal binders ruled out ion depletion as the mode of action. These results show that polymeric phage inhibitors may work by unique mechanisms of action and that pH alone cannot explain the observed effects whilst also placing constraints on the practical utility of poly(acrylic acid).

Radiation-induced nanogel engineering based on pectin for pH-responsive rutin delivery for cancer treatment.

This research investigates the formulation of a nanogel complex using pectin and poly(acrylic acid) (PAAc) to encapsulate rutin. The nanogel's pH-responsive behavior and its potential as a targeted drug delivery platform are investigated. The gamma irradiation-induced crosslinking mechanism is elucidated, highlighting its role in creating a stable three-dimensional network structure within the polymer matrix. Fourier transform infrared spectroscopy analysis sheds light on the molecular interactions within rutin and the nanogel-rutin complex. The pH-responsive behavior of the nanogel is explored, showcasing its ability to release rutin selectively in response to pH variations and displaying high physical and chemical stability. Transmission electron microscopy imaging provides visual insights into nanogel morphology and interactions. The cumulative drug content from the nanogel was 86.14 ± 2.61%. The pH-dependent release profile of the nanogel was examined, demonstrating selective rutin release in response to varying pH levels. Cytotoxicity studies were conducted against four human cancer cell lines-HepG2, A549, MCF-7, and HCT-116 showing significant reductions in IC50 values, indicating enhanced therapeutic efficacy. Additionally, molecular docking studies revealed strong binding interactions of rutin with VEGFR-2 and EGFRT790M. Our nanogel compound 5 significantly reduced the IC50 values for HepG2, A549, MCF-7, and HCT-116 cells by 58.19%, 81.29%, 71.81%, and 67.16%, respectively. Furthermore, it lowered the IC50 values for VEGFR-2 and EGFRT790M by 29.66% and 68.18%, respectively.

Cell Adhesion and Local Cytokine Control on Protein-Functionalized PNIPAM-co-AAc Hydrogel Microcarriers.

Achieving adequate cell densities remains a major challenge in establishing economic biotechnological and biomedical processes. A possible remedy is microcarrier-based cultivation in stirred-tank bioreactors (STBR), which offers a high surface-to-volume ratio, appropriate process control, and scalability. However, despite their potential, commercial microcarriers are currently limited to material systems featuring unnatural mechanical properties and low adaptability. Because matrix stiffness and ligand presentation impact phenotypical attributes, differentiation potential, and genetic stability, biotechnological processes can significantly benefit from microcarrier systems tailorable toward cell-type specific requirements. This study introduces hydrogel particles co-polymerized from poly(N-isopropylacrylamide) (PNIPAM) and acrylic acid (AAc) as a platform technology for cell expansion. The resulting microcarriers exhibit an adjustable extracellular matrix-like softness, an adaptable gel charge, and functional carboxyl groups, allowing electrostatic and covalent coupling of cell adhesive and cell fate-modulating proteins. These features enable the attachment and growth of L929 mouse fibroblast cells in static microtiter plates and dynamic STBR cultivations while also providing vital growth factors, such as interleukin-3, to myeloblast-like 32D cells over 20 days of cultivation. The study explores the effects of different educt compositions on cell-particle interactions and reveals that PNIPAM-co-AAc microcarriers can provide both covalently coupled and diffusively released cytokine to adjacentcells.

Cysteine Conjugation: An Approach to Obtain Polymers with Enhanced Muco- and Tissue Adhesion

The modification of polymers towards increasing their biocompatibility gathers the attention of scientists worldwide. Several strategies are used in this field, among which chemical post-polymerization modification has recently been the most explored. Particular attention revolves around polymer-L-cysteine (Cys) conjugates. Cys, a natural amino acid, contains reactive thiol, amine, and carboxyl moieties, allowing hydrogen bond formation and improved tissue adhesion when conjugated to polymers. Conjugation of Cys and its derivatives to polymers has been examined mostly for hyaluronic acid, chitosan, alginate, polyesters, polyurethanes, poly(ethylene glycol), poly(acrylic acid), polycarbophil, and carboxymethyl cellulose. It was shown that the conjugation of Cys and its derivatives to polymers significantly increased their tissue adhesion, particularly mucoadhesion, stability at physiological pH, drug encapsulation efficiency, drug release, and drug permeation. Conjugates were also non-toxic toward various cell lines. These properties make Cys conjugation a promising strategy for advancing polymer applications in drug delivery systems and tissue engineering. This review aims to provide an overview of these features and to present the conjugation of Cys and its derivatives as a modern and promising approach for enhancing polymer tissue adhesion and its application in the medical field.

Versatile synthesis of uniform mesoporous superparticles from stable monomicelle units.

Superstructures with architectural complexity and unique functionalities are promising for a variety of practical applications in many fields, including mechanics, sensing, photonics, catalysis, drug delivery and energy storage/conversion. In the past five years, a number of attempts have been made to build superparticles based on amphiphilic polymeric micelle units, but most have failed owing to their inherent poor stability. Determining how to stabilize micelles and control their superassembly is critical to obtaining the desired mesoporous superparticles. Here we provide a detailed procedure for the preparation of ultrastable polymeric monomicelle building units, the creation of a library of ultrasmall organic-inorganic nanohybrids, the modular superassembly of monomicelles into hierarchical superstructures and creation of novel multilevel mesoporous superstructures. The protocol enables precise control of the number of monomicelle units and the derived mesopores for superparticles. We show that ultrafine nanohybrids display enhanced mechanical antipressure performance compared with pristine polymeric micelles, and describe the functional characterization of mesoporous superstructures that exhibit excellent oxygen reduction reactivity. Except for the time (4.5 d) needed for the preparation of the triblock polystyrene-block-poly(4-vinylpyridine)-block-poly(ethylene oxide) PS-PVP-PEO or the polystyrene-block-poly(acrylic acid)-block-poly(ethylene oxide) (PS-PAA-PEO) copolymer, the synthesis of the ultrastable monomicelle, ultrafine organic-inorganic nanohybrids, hierarchical superstructures and mesoporous superparticles require ~6, 30, 8 and 24 h, respectively. The time needed for all characterizations and applications are 18 and 10 h, respectively.

Preparation of viscosity-reducing polycarboxylate superplasticizer (PCE) and its role in low water-to-cement ratio system

Owing to the low water-cement ratio (less than 0.25) of ultra-high-performance concrete (UHPC) materials, the system exhibits increased viscosity, diminished slurry flow, and challenges in pouring during the construction process, which compromise its workability. Consequently, the development of highly efficient viscosity-reducing polycarboxylate superplasticizer (PCE) is of paramount importance. In this study, we synthesized a series of viscosity-reducing polycarboxylate superplasticizers(JN-PCE) utilizing allyl polyethylene glycol ether (APEG), acrylic acid (AA), and sodium methallyl sulfonate (SMAS) as raw materials through the process of free radical polymerization. Fourier-transform infrared spectroscopy, nuclear magnetic resonance, gel permeation chromatography, and energy-dispersive X-ray spectroscopy were employed to characterize the materials. Subsequent evaluations of surface tension, fluidity, adsorption performance, and Marsh time demonstrated that these superplasticizers exhibited commendable dispersion and remarkable viscosity-reducing properties within a low water-cement ratio system. At a water-cement ratio of 0.18, the Marsh time of the JN-type PCE was reduced by 40% while maintaining the same fluidity, thereby underscoring the effective viscosity-reducing capabilities of the synthesized polycarboxylate superplasticizer.

Si anodes via dual strategies of coating Si with a rigid polymer and employing a polymer binder with improved mechanical properties

Si undergoes significant volume change over cycles which degrades the structural integrity and stability of the electrode. This volume change is the primary barrier to the commercialization of Si anodes, and it is more pronounced for Si particle sizes over 150 nm. In this study, a crosslinked polymer binder is developed using poly(acrylic acid-co-acrylamide) (PAAM) with enhanced elasticity compared to the widely used poly(acrylic acid). PAAM is further grafted with boronic acid and dopamine, yielding PAAM-B-D, a binder with improved adhesion due to its 3D crosslinked network. Additionally, 350-nm Si is coated with cyclized polyacrylonitrile (cPAN) and heat-treated to form a conjugated structure. The cPAN-coated Si (cSi) exhibits enhanced conductivity and mechanical stiffness and is used as an active material. The developed Si anode effectively combines cPAN-coated Si with the crosslinked network formed in the PAAM-B-D polymer for enhanced adhesion. The cSi@PAAM-B-D electrode sufficiently maintains its structural integrity and mitigates the Si volume change even with the large-sized 350-nm Si. The cSi@PAAM-B-D exhibits a high initial Coulombic efficiency of 86.5 %, at a Si mass loading of 2 mg cm−2. It also shows a capacity retention of 83.6 % and a high areal capacity of 3 mAh cm−2 after 50 cycles.

Triple-template surface imprinted magnetic polymers for wide-coverage extraction of steroid hormones from human serum.

In this study, novel triple-template magnetic nanospheres by surface imprinting, called triple-template magnetic molecularly imprinted polymers (tri-MMIPs), were prepared for the detection of steroid hormones in human serum. The polymers were constructed by Fe3O4 as support, estrone (E1), progesterone (PROG), and estradiol (E2) as triple templates, acrylic acid (AA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker. The resulting tri-MMIPs were further characterized and applied as sorbents in human serum pretreatment. Coupled with ultra-high performance liquid chromatography-triple quadrupole tandem mass spectrometry (UHPLC-MS/MS) profiling after derivatization, 15 steroids (E1, 6-ketoE1, 4-OHE1, 16α-OHE1, DHEA, 4-MeOE1, PROG, PREG, 17-OHPROG, 7-DHE2, E2, 2-OHE2, 16-epiE3, E3, 2-MeOE2) were successfully quantified. The developed method exhibited a good recovery (78.9-114%) and low limit of quantitation (LLOQ, 5-10pg/mL), which indicates a great potential for application in the analysis of multiple steroid hormones in complex biological samples.

Localized Thermoresponsive Behavior in P(NIPAm‐co‐AAc) Copolymers: Structural Insights From Rheology and Small Angle X‐Ray Scattering

ABSTRACTStimuli‐responsive polymers stand out for their ability to respond to small environmental changes. One of the most representative thermo‐sensitive materials is poly(N‐isopropyl acrylamide) (PNIPAm), which presents reversible phase transitions close to the human body temperature. However, previous studies observed that the copolymerization of NIPAm with small quantities of different monomers like acrylic acid (AAc) results in copolymers with reduced or lost thermo‐responsivity. In this study, thermo‐sensitive PNIPAm, pH‐sensitive poly(acrylic acid) (PAAc), and various proportions of their copolymers P(NIPAm‐co‐AAc) were obtained by free radical polymerization and thoroughly characterized. Rheological and structural studies reveal the remaining thermosensitivity of the copolymers manifested at short molecular ranges. These alterations in short‐range interactions are observed in all samples containing NIPAm, and they are evidenced by changes in the fractality of their structure and flow index behavior of the Viscosity Ostwald–de Waele Model. Particularly, when the copolymer proportion of NIPAm/AAc is about 40/60, the Beaucage model reveals two structural levels, ~200 and ~10 nm. Furthermore, the model exhibits a thermal response of the lower‐size substructures, indicating possible segregation of NIPAm‐rich regions from copolymer chains. The evidence found in this work could contribute to the development of nanosystems, in which local thermoresponsive effects are sought, such as for active drug targeting.

Magnesium Fluoride Interlayers Enabled by Wet‐Chemical Process for High‐Performance Solid‐State Batteries

AbstractGarnet‐type solid‐state electrolytes (SSEs) exemplified by Li6.5La3Zr1.5Ta0.5O12 (LLZT) are chemically unstable when exposed to air, leading to the formation of impurities and poor wettability with Li metal. Herein, a protocol to address this Li/LLZT interface challenge is demonstrated by constructing a lithiophilic MgF2 nanofilm on the LLZT pellet. Specifically, a solution‐based process is developed for the surface engineering of LLZT, utilizing magnesium trifluoroacetate (MTF) as the molecular precursor while poly(acrylic acid) (PAA) as the coordinating agent in a sol‐gel process. It is demonstrated that a facile spin‐coating treatment followed by high‐temperature annealing reliably forms crack‐free MgF2 nanofilms with precise thickness control. Introduction an MgF2 interlayer transforms the LLZT pellet into a highly lithophilic, facilitating close contact with the lithium anode, thereby leading to a significantly reduced interfacial resistance from 1190 Ω cm2 to 6 Ω cm2. Such an interfacial engineering enables stable cycling of full batteries with high reversibility and rate capability using commercial LiFePO4 and LiNi0.83Co0.07Mn0.1O2 as cathodes. This study unfolds the possibility of a solution‐based method as a facile and scalable process for the construction of fluoride nanofilms, which is promising to address the critical interfacial challenges of solid‐state batteries (SSBs) to facilitate its practical applications.

High-Strength, Self-Healing Copolymers of Acrylamide and Acrylic Acid with Co(II), Ni(II), and Cu(II) Complexes of 4′-Phenyl-2,2′:6′,2″-terpyridine: Preparation, Structure, Properties, and Autonomous and pH-Triggered Healing

The utilization of self-healing polymers is a promising way of solving problems associated with the wear and tear of polymer products, such as those caused by mechanical stress or environmental factors. In this study, a series of novel self-healing, high-strength copolymers of acrylamide, acrylic acid, and novel acrylic complexes of 4′-phenyl-2,2′:6′,2″-terpyridine [Co(II), Ni(II), and Cu(II)] was prepared. A systematic study of the composition and properties of the obtained polymers was carried out using a variety of physicochemical techniques (elemental analysis, gel permeation chromatography (GPC), attenuated total reflectance Fourier transform infrared spectroscopy (ATR/FT-IR), ultraviolet-visible spectroscopy (UV-vis), small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), confocal laser scanning microscopy (CLSM), and tensile testing). All metallopolymer samples exhibit autonomous intrinsic healing along with maintaining high tensile strength values (for some samples, the initial tensile strength exceeded 100 MPa). The best values of healing efficiency are possessed by metallopolymers with a nickel complex (up to 83%), which is most likely due to the highest lability of the metal–heteroatom coordination bonds. The example of this system shows the ability to re-heal with negligible deterioration of the mechanical properties. The possibility of tuning the mechanical properties of self-healing films through the use of different metal ions has been demonstrated.