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The article discusses the integration of 3D printing technology into chemistry lessons, highlighting its benefits in creating high-quality teaching materials and educational games at a lower cost. It explores the use of 3D printing as a learning tool to understand plastics and resin printers, promoting digital skills relevant for teachers and students. The article also delves into the process of creating 3D-printed objects and the chemical background of resin printing, focusing on the application of radical polymerization in the classroom. [Extracted from the article]

We report the results of an international interlaboratory study of the flexural strength of alumina fabricated across six laboratories using the vat photopolymerization ceramic additive manufacturing (AM) technology. The mechanical testing of all the specimens, 142 in total, was performed at the National Institute of Standards and Technology (NIST) according to the well‐established four‐point bending method standardized for traditional ceramics. Overall, the existing ASTM standard for the four‐point bend testing proved adequate for AM ceramics, with several modifications to the specimen requirements to account for the specifics of AM processes. Critical flaws that caused failure were identified in all but two cases using optical fractography augmented with the imaging of fracture surfaces in a scanning electron microscope. The flexural strength data, analyzed following the Weibull statistics, exhibited considerable variation among the specimen sets manufactured by different laboratories. This variability correlated with the presence of many distinct critical flaws. We identified seven types of flaws that accounted for the failure of 94% of specimens. The prevalent flaws depend on the printing direction relative to the specimen's geometry. We discuss the nature of these flaws and their relation to the printing and post‐processing conditions. Removal of several types of critical flaws will significantly improve mechanical properties of ceramic parts built using vat‐photopolymerization AM. [ABSTRACT FROM AUTHOR]

The photoATRP of methyl acrylate (MA) is investigated using riboflavin (RF) and CuBr2/Me6TREN as a dual catalyst system under green LED irradiation (λ ≈ 525 nm). Both RF and CuBr2/Me6TREN enhanced oxygen tolerance, enabling effective ATRP in the presence of residual oxygen. High molar mass polymers (up to Mn ≈ 129 000 g·mol−1) with low dispersity (Đ ≤ 1.16) are prepared, and chain‐end fidelity is confirmed through successful chain extension. The molecular masses of the obtained polymer increased linearly with conversion and showed high initiation efficiency. Mechanistic studies by laser flash photolysis reveal that the predominant activator generation mechanism is reductive quenching of RF by Me6TREN (83%, under [CuBr2]/[Me6TREN] = 1/3 condition), supported by polymerization kinetics and thermodynamic calculations. [ABSTRACT FROM AUTHOR]

This paper introduces an approach to preparing high‐strength Si3N4 ceramics using vat photopolymerization with a bi‐phase particle size gradation strategy. The influence of different ratios of coarse β‐Si3N4 powders (Cβ) and fine α‐Si3N4 powders (Fα) on the slurry performance, microstructure evolution, and final ceramic strength was systematically studied. It was found that an appropriate particle size gradation can significantly reduce the viscosity of the slurry. The curing depth of Si3N4 slurries decreases with increasing Fα content, while the stability increases. During sintering, dissolved Fα‐Si3N4 not only directly precipitates into small elongated β‐Si3N4 grains but also onto the neighboring Cβ‐Si3N4, promoting the development of large elongated β‐Si3N4 grains and resulting in a bimodal microstructure distribution. The highest strength of Si3N4 ceramics was achieved with a ratio of 6:4 Cβ to Fα Si3N4 powders. Under these conditions, the Si3N4 ceramics exhibited a flexural strength of 472 MPa, significantly higher than that of Si3N4 ceramics prepared using pure Cβ/Fα powders. The strength improvement is primarily due to the well‐designed bi‐phase particle size gradation strategy, which optimizes slurry performance, minimizes defects that may be introduced during the green part printing process while controlling the microstructure evolution during sintering, achieves the ideal bimodal microstructure distribution. The outcomes of this research demonstrate the feasibility of using vat photopolymerization with bi‐phase particle size gradation for the preparation of high‐strength Si3N4 ceramics, which has great potential for application in the manufacturing of various ceramic products. [ABSTRACT FROM AUTHOR]

Integration of lead‐halide perovskite quantum dots (PQDs) into full‐color microarrays presents numerous advantages for full‐color micro‐LED displays. There is an urgent requirement for a new design approach that simplifies the creation of durable PQD/polymer composites to produce stable PQD microarrays. Here, mono‐2‐(methacryloyloxy)ethyl succinate (MMeS) is utilized as a functional ligand to synthesize green MMeS‐modified CsPbBr3 PQDs (M‐CPB PQDs). The subsequent photopolymerization of M‐CPB PQDs with 1,6‐hexanediol diacrylate (HDDA) forms a CsPbBr3 PQD/polymer composite. This composite exhibits a solid‐state photoluminescence quantum yield of 73.1%, and the photoluminescence intensity retains 72% of its original value after 17 days of continuous immersion in water. Stable green PQD/polymer microarrays can be printed using an ink containing M‐CPB PQDs, HDDA, diphenyl (2,4,6‐trimethylbenzoyl) phosphine oxide, and n‐dodecane via electrohydrodynamic jet printing and in situ polymerization under UV light irradiation. Full‐color patterns can also be generated with MMeS‐modified red, green, and blue PQDs. These findings highlight the critical role of functionalizing the surface ligands of PQDs to improve their processability, thereby facilitating the development of stable PQD/polymer microarrays. [ABSTRACT FROM AUTHOR]

Alternating copolymers are crucial for diverse applications. While dispersity (Ð, also known as molecular weight distribution, MWD) influences the properties of polymers, achieving low dispersities in alternating copolymers poses a notable challenge via free radical polymerizations (FRPs). In this work, we demonstrated an unexpected discovery that dispersities are affected by the participation of charge transfer complexes (CTCs) formed between monomer pairs during free radical alternating copolymerization, which have inspired the successful synthesis of various alternating copolymers with low dispersities (>30 examples, Ð=1.13–1.39) under visible‐light irradiation. The synthetic method is compatible with binary, ternary and quaternary alternating copolymerizations and is expandable for both fluorinated and non‐fluorinated monomer pairs. DFT calculations combined with model experiments indicated that CTC‐absent reaction exhibits higher propagation rates and affords fewer radical terminations, which could contribute to low dispersities. Based on the integration of Monte Carlo simulation and Bayesian optimization, we established the relationship map between FRP parameter space and dispersity, further suggested the correlation between low dispersities and higher propagation rates. Our research sheds light on dispersity control via FRPs and creates a novel platform to investigate polymer dispersity through machine learning. [ABSTRACT FROM AUTHOR]

Functional polyvinylethylene glycols (PVEGs) with pendent vinyl groups were synthesized by Pd/B synergistic catalysts and their structures were characterized by 1H NMR and FT‐IR. The photopolymerization of the obtained PVEGs with multifunctional thiols in the presence of a photoinitiator proceeded smoothly via thiol‐ene photo‐click reaction to give a series of crosslinked materials by the variation of the molecular weight of PVEGs and a ratio of thiols and enes. The curing behavior was studied by FT‐IR and the properties of crosslinked materials were characterized by the test of gel content, swelling ratio, and water absorption. The dynamic mechanical analysis, mechanical properties, thermogravimetry, and surface properties of the crosslinked materials were investigated and the performance of coating for the crosslinked film materials was also characterized. The crosslinked film materials can be further functionalized by post‐crosslinking modification through thiol‐ene photo‐click reaction. [ABSTRACT FROM AUTHOR]

Solvent‐free photopolymerization of vinyl monomers to produce high modulus materials with applications in 3D printing and photoswitchable materials is demonstrated. Polymerizable eutectic (PE) mixtures are prepared by simply heating and stirring various molar ratios of N‐isopropylacrylamide (NIPAM), acrylamide (AAm) and 2‐hydroxyethyl methacrylate (HEMA). The structural and thermal properties of the resulting mixtures are evaluated by 1D and 2D NMR spectroscopy as well as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). UV photocuring kinetics of the PE mixtures is evaluated via in situ photo‐DSC and photorheology measurements. The PE mixtures cure rapidly and display storage moduli that are orders of magnitude greater than equivalent copolymers cured in an aqueous medium. The versatility of these PE systems is demonstrated through the addition of a photoswitchable spiropyran acrylate monomer, as well as applying the PE formulation as a stereolithography (SLA)‐based 3D printing resin. Due to the hydrogen‐bonding network in PE systems, 3D printing of the eutectic resin is possible in the absence of crosslinkers. The addition of a RAFT agent to reduce average polymer chain length enables 3D printing of materials which retain their shape and can be dissolved on demand in appropriate solvents. [ABSTRACT FROM AUTHOR]

Hydrogel actuators with complex 3D initial shapes show numerous important applications, but it remains challenging to fabricate such actuators. This article describes a polyelectrolyte‐based strategy for modulating small‐scale internal stresses within hydrogels to construct complex actuators with tailored 3D initial shapes. Introducing polyelectrolytes into precursor solutions significantly enhances the volume shrinkage of hydrogel networks during polymerization, allowing us to modulate internal stresses. Photopolymerization of these polyelectrolyte‐containing solutions through a mask produces mechanically strong hydrogel sheets with large patterned internal stresses. Consequently, these hydrogel sheets attain complex 3D initial shapes at equilibrium, in contrast to the planar initial configuration of 2D actuators. We demonstrate that these 3D actuators can reversibly transform into other 3D shapes (i.e. 3D‐to‐3D shape transformations) in response to external stimuli. Additionally, we develop a predictive model based on the Flory‐Rehner theory to analyze the polyelectrolyte‐mediated shrinking behaviors of hydrogel networks during polymerization, allowing precise modulation of shrinkage and internal stress. This polyelectrolyte‐boosted shrinking mechanism paves a route to the fabrication of high‐performance 3D hydrogel actuators. [ABSTRACT FROM AUTHOR]

NIR‐induced upconversion‐assisted photopolymerization has gained growing attention in the past two decades because of its numerous advantages over conventional UV/visible photopolymerization and two‐photon polymerization processes. However, research in this area is still in its early stages. To extend the practical application of NIR‐induced radiation curing, it is essential to optimize the factors affecting the photopolymerization reactions. Researchers have been constantly trying to improve these factors to tune the photo‐physical characteristics (luminescence intensity and color) of upconversion particles (UCPs), enhance curing depths and degree of double bond conversion (DC), and investigate the application of UCPs in emerging fields. In this review, first, a brief discussion of the upconversion mechanisms and upconversion efficiency is provided. Then, a detailed discussion of the factors influencing the upconversion‐assisted photopolymerization comprising UCP nature and characteristics, UCP content, presence of fillers/pigments/additives, laser intensity, photoinitiator content, and maximum absorption wavelength of photoinitiator is provided, and recent progress in improving these factors is presented. Finally, the advantages and drawbacks of the UC‐initiated polymerization are discussed, and perspectives for future directions are suggested. Highlights: NIR‐induced upconversion‐assisted photopolymerization garners growing interest.Influential factors in upconversion‐assisted photopolymerization are thoroughly discussed.The recent progress on improving these factors and the future directions are provided. [ABSTRACT FROM AUTHOR]

The use of photopolymerization is expanding across a multitude of biomedical applications, from drug delivery to bioprinting. Many of these current and emerging photopolymerization systems employ visible light, as motivated by safety and energy efficiency considerations. However, the "library" of visible light initiators is limited compared with the wealth of options available for UV polymerization. Furthermore, the synthesis of traditional photoinitiators relies on diminishing raw materials, and several traditional photoinitiators are considered emerging environmental contaminants. As such, there has been recent focus on identifying and characterizing biologically sourced, visible light‐based photoinitiator systems that can be effectively used in photopolymerization applications. In this regard, several bio‐sourced molecules have been shown to act as photoinitiators, primarily through Type II photoinitiation mechanisms. However, whether bio‐sourced molecules can also act as effective synergists in these reactions remains unknown. In this study, we evaluated the effectiveness of bio‐sourced synergist candidates, with a focus on amino acids, due to their amine functional groups, in combination with two bio‐sourced photoinitiator molecules: riboflavin and curcumin. We tested the effectiveness of these photoinitiator systems under both violet (405 nm) and blue (460–475 nm) light using photo‐rheology. We found that several synergist candidates, namely lysine, arginine, and histidine, increased the polymerization effectiveness of riboflavin when used with both violet and blue light. With curcumin, we found that almost all tested synergist candidates slightly decreased the polymerization effectiveness compared with curcumin alone under both light sources. These results show that bio‐sourced molecules have the potential to be used as synergists with bio‐sourced photoinitiators in visible light photopolymerization. However, more work must be done to fully characterize these reactions and to investigate more synergist candidates. Ultimately, this information is expected to expand the range of available visible light‐based photoinitiator systems and increase their sustainability. [ABSTRACT FROM AUTHOR]

Viologen‐based reactive mesogen (VRM) is newly designed and synthesized for the development of polarization‐dependent, color‐tunable, and transparent electrochromic (EC) smart windows. By controlling electric field, the color of VRM can be intentionally tuned due to the formation of dication (D state), cation‐radical (C state), and neutral state (N state). Based on the deep understanding of phase transition of VRM, a uniaxially oriented VRM hierarchical nanostructure is successfully constructed on the macroscopic area by simple coating and self‐assembly processes. The subsequent photopolymerization significantly improves thermal, mechanical, and chemical stabilities of the VRM thin film. In addition to the control of color, the transmittance of uniaxially oriented VRM‐based EC smart window can be precisely tuned by rotating a linear polarizer. [ABSTRACT FROM AUTHOR]

4D printing has attracted widespread attention due to its ability to fabricate complex structures capable of responding to specific stimuli. However, existing smart materials used for 4D printing, such as conventional hydrogels, liquid crystal elastomers, and shape‐memory polymers, are constrained in their ability to fulfill both mechanical ultrastrength and ultrastretchability requirements simultaneously due to their water saturation or uneven network structures. This study presents 4D printing of liquid‐free ionic elastomers (LFIEs) that is achieved through photopolymerization of the acrylic acid‐tetramethylammonium chloride‐polymerizable deep eutectic solvent. The transition temperature (Tt) of the high‐fracture‐strength LFIEs is adjusted by introducing phenylphosphoric acid, harboring multiple hydrogen‐bonds, leading to improved molecular chain mobility through softening of the chains. Consequently, the 4D‐printed LFIEs retain their high strength while achieving ultrastretchable properties even under elevated temperatures during heating. Moreover, the 4D‐printed LFIEs demonstrate both a swift response time and a high fixation rate even after undergoing repeated transformation cycles. These outstanding capabilities exhibit by LFIEs present a reliable strategy for advancing their applications in diverse fields, such as smart furniture, robotics, and intelligent manufacturing with remote monitoring, and beyond. [ABSTRACT FROM AUTHOR]

Sulfur dots (S‐dots) eliminate the need of expensive and toxic conventional photocatalysts or transition metal in photoinduced reversible deactivation radical polymerization (photoRDRP). Herein, non‐metallic S‐dots mediated photoRDRP of N,N‐dimethyl acrylamide (DMA) are developed for the first time. This technique allows for the precise synthesis of narrow‐dispersed poly(N,N‐dimethyl acrylamide) (PDMA) and double hydrophilic poly(N, N‐dimethyl acrylamide)‐block‐poly(2‐hydroxyethyl acrylamide) (PDMA‐b‐PHEAA) diblock copolymer suitable for contaminant removal from water. Also, its subsequent modification into a poly(N,N‐dimethyl acrylamide)‐block‐poly(N‐(2‐((4‐vinylbenzyl)oxy)ethyl)acrylamide) (PDMA‐b‐PVBEAA) diblock copolymer gives ultra‐fast gelation and production of writable ink‐gel, which is exceptionally well‐suited for 3D printing applications, enabling the creation of precise and defined shapes. This innovative material serves as an intriguing scaffold for tissue engineering and other biomaterial applications, especially in areas that demand rapid and customizable manufacturing solutions. [ABSTRACT FROM AUTHOR]

Sustainable carbon dots based on cellulose, particularly carboxymethyl cellulose carbon dots (CMCCDs), were confined in an inorganic network resulting in CMCCDs@SiO2. This resulted in a material exhibiting long afterglow covering a time frame of several seconds also under air. Temperature‐dependent emission spectra gave information on thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) while photocurrent experiments provided a deeper understanding of charge availability in the dark period, and therefore, its availability on the photocatalyst surface. The photo‐ATRP initiator, ethyl α‐bromophenylacetate (EBPA), quenched the emission from the millisecond to the nanosecond time frame indicating participation of the triplet state in photoinduced electron transfer (PET). Both free radical and controlled radical polymerization based on photo‐ATRP protocol worked successfully. Metal‐free photo‐ATRP resulted in chain extendable macroinitiators based on a reductive mechanism with either MMA or in combination with styrene. Addition of 9 ppm Cu2+ resulted in Mw/Mn of 1.4 while an increase to 72 ppm improved uniformity of the polymers; that is Mw/Mn=1.03. Complementary experiments with kerria laca carbon dots confined materials, namely KCDs@SiO2, provided similar results. Deposition of Cu2+ (9 ppm) on the photocatalyst surface explains better uniformity of the polymers formed in the ATRP protocol. [ABSTRACT FROM AUTHOR]

The triplet excited state lifetime of a photosensitizer is an essential parameter for diffusion‐controlled energy‐ and electron‐transfer, which occurs usually in a competitive manner to the intrinsic decay of a triplet excited state. Here we show the decisive role of luminescence lifetime in the triplet excited state reactivity toward energy‐ and electron transfer. Anchoring two phenyl anthracene chromophores to a ruthenium(II) polypyridyl complex (RuII ref) leads to a RuII triad with a luminescence lifetime above 100 μs, which is more than 40 times longer than that of the prototypical complex. The obtained RuII triad sensitizes energy transfer to anthracene‐based annihilators more efficiently than RuII ref and enables red‐to‐blue photon upconversion with a pseudo anti‐Stokes shift of 0.94 eV and a moderate upconversion efficiency near 1 % in aerated solution. Particularly, RuII triad allows rapid photoredox catalytic polymerizations of acrylate and acrylamide monomers under aerobic condition with red light, which are kinetically hindered for RuII ref. Our work shows that excited state lifetime of a photosensitizer governs the dynamics of the excited state reactions, which seems an overlooked but important aspect for photochemistry. [ABSTRACT FROM AUTHOR]

Highlights This study is dedicated to the fabrication of acrylated epoxidized natural rubber (AENR)/dual‐functionalized organoclay (DF‐C30B) hybrid networks using an in‐situ light‐induced crosslinking polymerization technique. The process begins with the successful synthesis of DF‐C30B, which contains methacrylate groups, achieved by reacting 3‐methacryloxypropyltrimethoxysilane (MPS) with cloisite 30B (C30B). During fabrication, DF‐C30B nanolayers are dispersed within the AENR matrix at various feed ratios, ranging from 1 to 8 parts per hundred of rubber (phr). The photocrosslinking polymerization is then initiated using 2,2‐dimethoxy‐2‐phenylacetophenone (DMPA) as the photoinitiating agent. Subsequent analysis of the nanocomposites involves evaluating their structure and morphology using established techniques such as Fourier transform infrared (FTIR) spectroscopy, x‐ray diffraction (XRD), thermogravimetric analysis (TGA), and transmission electron microscopy (TEM). The FTIR analysis enables comparing distinct bands of the nanocomposite's components, affirming the integration and covalent attachment of nanoclay in the AENR matrix. Results from TEM and XRD illustrate the uniform distribution of DF‐C30B throughout the AENR matrix without significant agglomeration. TGA results indicate that the hybrid networks exhibit enhanced thermal stability, with degradation onset temperatures of 306°C, 308°C, 315°C, and 318°C for DF‐C30B loadings of 1, 2, 4, and 8 phr, respectively, compared to 198°C for pure AENR. Correspondingly, char residue levels increased to 4.3%, 5.6%, 7.8%, and 11.7% for the respective DF‐C30B contents. This research underscores the promising role of DF‐C30B as a strengthening component in nanocomposites based on NR, contributing to improved thermal endurance, enhanced uniformity, and offering insightful directions for future advancements. Fabricated acrylated epoxidized natural rubber (AENR)/dual‐functionalized organoclay (DF‐C30B) hybrid networks via light‐induced crosslinking polymerization. Enhanced compatibility and performance of DF‐C30B within the AENR matrix. Successful integration and stability confirmed by Fourier transform infrared spectroscopy, x‐ray diffraction (XRD), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Uniform dispersion of DF‐C30B within the matrix demonstrated by XRD and TEM. Improved thermal stability compared to neat AENR, as evidenced by TGA results. [ABSTRACT FROM AUTHOR]

Polymerization in the solid state is generally infeasible due to restrictions on mobility. However, in this work, the solid‐state photopolymerization of crystalline dicyclopentadiene is demonstrated via photoinitiated ring‐opening metathesis polymerization. The source of mobility in the solid state is attributed to the plastic crystal nature of dicyclopentadiene, which yields local short‐range mobility due to orientational degrees of freedom. Polymerization in the solid state enables photopatterning, volumetric additive manufacturing of free‐standing structures, and fabrication with embedded components. Solid‐state photopolymerization of dicyclopentadiene offers a new paradigm for advanced and freeform fabrication of high‐performance thermosets. [ABSTRACT FROM AUTHOR]

A material capable of curing due to UV irradiation based on an alkyd oligomer and oligoorganosilsesquioxanes (OOSs) with functional thiol groups was obtained. Using microinterferometry, it was shown that the alkyd oligomer and OOS are completely compatible (mutually soluble). The resulting alkyd‐siloxane composition was cured under the action of UV irradiation due to reaction between double bonds of alkyd oligomer and thiol‐groups of silsesquioxane oligomer. The curing reaction takes 5 min with formation of coating, containing 99% of gel fraction, which is in 30 times faster in comparison with the classical method of alkyd curing in the presence of siccatives. The hydrophobicity of alkyd‐siloxane coatings also increases and varies depending on the content of OOS. The introduction of 50% OOS into the alkyd oligomer makes it possible to increase the water contact angle by 10° relative to the coating based on pure alkyd. A similar dependence is observed when studying the thermal stability of coatings. Thus, even with the introduction of 10% OOS into alkyd oligomer, the temperature at which a loss of 50% of mass occurs increases by 24°C relative to coatings based on a pure alkyd oligomer. [ABSTRACT FROM AUTHOR]

We report an anomalous structural transformation of a Cu(I) cluster into two different types of copper‐silver (CuAg) alloy nanoclusters. Different from previous reports, we demonstrate that under specifically designed reaction conditions, the Ag‐doping could induce a substantial growth of the starting Cu15 and a Ag13Cu20 nanocluster was obtained via the unexpected insertion of an Ag13 kernel inside the Cu(I)‐S shell. Ag13Cu20 demonstrates high activity to initiate the photopolymerization of previously hard‐to‐print inorganic polymers in 3D laser microprinting. Interestingly, a slight modification of the reaction condition leads to the formation of another Ag18‐xCuxS (8≤x) nanocluster templated by a central S2− anion, which possesses a unique electronic structure compared to conventional template‐free CuAg nanoclusters. Overall, this work unveils the intriguing doping chemistry of Cu clusters, as well as their capability to create different types of alloy nanoclusters with previously unobtainable structures and multifunctionality. [ABSTRACT FROM AUTHOR]

Controlled radical polymerization (CRP) techniques enable the preparation of diverse, chemically tailored polymers with a variety of chain architectures. Separately, light‐mediated polymerization reactions offer a number of advantages over thermal polymerizations in terms of energy efficiency, sustainability, and versatility. Recent work has combined photopolymerization and CRP techniques to advance the synthesis of polymers with nonlinear architectures, including bottlebrush polymers, star polymers, hyperbranched polymers, and cyclic polymers. These photoCRP methods offer novel routes to nonlinear polymers using mild reaction conditions. In this review, we provide an overview of photoCRP techniques for the synthesis of nonlinear polymers. We start with a discussion of photoCRP applied to the synthesis of linear polymers and discuss the underlying reaction mechanisms. Then, we discuss photoCRP applied to the synthesis of bottlebrush, star, hyperbranched, cyclic, and surface‐initiated polymer brushes. For each case, we discuss the synthetic strategy and the unique properties and characteristics of the resulting polymers, and we provide a perspective on potential future directions for research. [ABSTRACT FROM AUTHOR]

Vanillyl alcohol has emerged as a widely used building block for the development of biobased monomers. More specifically, the cationic (photo‐)polymerization of the respective diglycidyl ether (DGEVA) is known to produce materials of outstanding thermomechanical performance. Generally, chain transfer agents (CTAs) are of interest in cationic resins not only because they lead to more homogeneous polymer networks but also because they strikingly improve the polymerization speed. Herein, the aim is to compare the cationic chain‐growth photopolymerization with the thermally initiated anionic step‐growth polymerization, with and without the addition of CTAs. Indeed, CTAs lead to faster polymerization reactions as well as the formation of more homogeneous networks, especially in the case of the thermal anionic step‐growth polymerization. Resulting from curing above the TG of the respective anionic step‐growth polymer, materials with outstanding tensile toughness (>5 MJ cm−3) are obtained that result in the manufacture of potential shape‐memory polymers. [ABSTRACT FROM AUTHOR]

In this work, six benzothioxanthene‐based oxime esters were employed as photoinitiators for photopolymerization under visible light (LED) and sunlight. Their abilities to behave as Type I photoinitiators by mean of a photocleavage mechanism of oxime esters but also in multicomponent photoinitiating systems with an iodonium salt (through an electron transfer mechanism) were both explored with the different structures. Due to their broad absorption spectra tailing up 600 nm, photoinitiating properties of the benzothioxanthene‐based oxime esters were systematically tested under excitation with low‐intensity LED light at wavelengths of 405 nm and 450 nm. Additionally, parallel to the polymerization tests done under artificial light, the different benzothioxanthene‐based oxime esters were also investigated as solar photoinitiators and displayed a high reactivity in France (Western Europe) even in winter conditions. For the best candidates i.e. the most reactive structures, direct laser write experiments were carried out, evidencing the interest of these structures. [ABSTRACT FROM AUTHOR]

A new type polymeric adsorbent, poly(allylphenol‐co‐hydroxyethyl methacrylate‐co‐vinyl imidazole) (PAHV), is synthesized in this study. 2‐Hydroxyethyl methacrylate is used as complementary monomers along with 1‐vinyl imidazole and allylphenol monomers. The photopolymerization method is preferred as a synthesis method and benzophenone is used as the photoinitiator. The effectiveness of the PAHV against bacterial species such as Escherichia coli and Staphylococcus aureus is investigated by the Clinical and Laboratory Standards Institute (CLSI) disk diffusion method. The inhibition areas of PA1H1V3 and PA1H1V1 derivatives against E. coli and S. aureus are measured as 25 mm ± 0.25 mm and 7 mm ± 0.1 mm; 20 mm ± 0.25 mm, and 5 mm ± 0.1 mm, respectively. Sorption efficiencies (%) at pH = 6 (selected optimum pH) for 100 μg/L Cd and Cr of the PA1H1V1, PA1H3V1, and PA1H1V3 derivatives are found to be 69.0 ± 2.7 and 58.3 ± 6.7, 66.8 ± 6.2 and 75.8 ± 5.5, and 97.2 ± 3.7 and 97.7 ± 3.2 (n = 3), respectively. Adsorption studies revealed that the PA1H1V3 polymer can be used as an alternative for the sorption of cadmium and chromium. The pseudo‐second‐order model and Langmuir isotherm model fits for both adsorption processes. The adsorption capacities obtained from the Langmuir isotherm model for chromium and cadmium sorption are 52.63 and 68.49 μg g−1, respectively. [ABSTRACT FROM AUTHOR]

Trees grow by coupling the transpiration‐induced nutrient absorption from external sources and photosynthesis‐based nutrient integration. Inspired by this manner, we designed a class of polyion complex (PIC) hydrogels containing isolated liquid‐filled voids for growing texture surfaces. The isolated liquid‐filled voids were created via irreversible matrix reconfiguration in a deswelling‐swelling process. During transpiration, these voids reversibly collapse to generate negative pressures within the matrices to extract polymerizable compounds from external sources and deliver them to the surface of the samples for photopolymerization. This growth process is spatial‐controllable and can be applied to fabricate complex patterns consisting of different compositions, suggesting a new strategy for making texture surfaces. [ABSTRACT FROM AUTHOR]

Bottlebrush polymers have a variety of useful properties including a high entanglement molecular weight, low Young's modulus, and rapid kinetics for self‐assembly. However, the translation of bottlebrushes to real‐world applications is limited by complex, multi‐step synthetic pathways and polymerization reactions that rely on air‐sensitive catalysts. Additionally, most bottlebrushes are non‐degradable. Herein, we report an inexpensive, versatile, and simple approach to synthesize degradable bottlebrush polymers under mild reaction conditions. Our approach relies on the “grafting‐through” polymerization of α‐lipoic acid (LA)‐functionalized macromonomers. These macromonomers can be polymerized under mild, catalyst‐free conditions, and due to reversibility of the disulfide bond in LA, the resulting bottlebrush polymers can be depolymerized by cleaving disulfide backbone bonds. Bottlebrushes with various side‐chain chemistries can be prepared through the atom transfer radical polymerization (ATRP) of LA‐functionalized macromonomers, and the backbone length is governed by the macromonomer molecular weight and solvent polarity. We also demonstrate that LA‐functionalized macromonomers can be copolymerized with acrylates to form degradable bottlebrush networks. This work demonstrates the preparation of degradable bottlebrush polymers with a variety of side‐chain chemistries and provides insight into the light‐mediated grafting‐through polymerization of dithiolane‐functionalized macromonomers. [ABSTRACT FROM AUTHOR]

Two coumarinacyl bromides, 3‐(bromoacetyl)coumarin (BAC) and 3‐(bromoacetyl)‐7‐methoxycoumarin (BACO), were developed for the photopolymerization of N‐ethylcarbazole to construct conjugated polymer under visible and near‐infrared light irradiation. BAC outperformed the conventional phenacyl bromide photoinitiator, exhibiting superior photoinitiation performance due to its optimal absorption characteristics and electron transfer efficiency. The obtained poly(N‐ethylcarbazole) was thoroughly characterized, demonstrating the successful synthesis of a conjugated polymer with desired properties. Dedoping led to improved optical properties and film morphology. The polymerization mechanism was elucidated using transient absorption spectroscopy, revealing efficient electron transfer from the excited photoinitiators to N‐ethylcarbazole. [ABSTRACT FROM AUTHOR]

Functionally graded materials (FGMs) have spatial variations in structure or composition that result in gradients in their mechanical, thermal, swelling, or other properties. FGMs have garnered significant research interest because of their extensive applications in areas such as biomedical implants, sensors, and soft robotics. Recently, grayscale photopolymerization 3D printing has emerged as a promising technology for crafting complex and high‐resolution FGMs. This comprehensive work delves into various grayscale photopolymerization 3D printing techniques, offering insights into their ability to precisely control printing exposure energy and polymerization degree, which in turn influence material properties. Furthermore, this work highlights diverse applications of grayscale vat‐photopolymerization 3D printing. Finally, it offers perspectives on ways to enhance grayscale photopolymerization 3D printing, with a focus on improving printing feedstocks and grayscale strategies. [ABSTRACT FROM AUTHOR]

Rapid manufacturing of medical devices during unforeseen pandemics is imperative. In striving for manufacturing efficiency, photopolymerization has emerged as a viable approach for diverse healthcare applications in recent decades. Photopolymerization‐based 3D printing offers significant potential with a range of biocompatible materials (e.g., poly(ethylene glycol), cellulose, etc.) while minimizing waste generation. However, prevalent commercial photoinitiators used in this process are synthetic and environmentally unfriendly. Therefore, the naturally occurring and derived photoinitiators have drawn tremendous research interest due to their bioactivities and inherent environmental safety. This review comprehensively outlines the medical applications implemented by these photoinitiators, highlighting their inherent photoinitiation abilities. Moreover, it delves into the impact of substituent effects on the photoinitiation abilities of naturally derived photoinitiators. [ABSTRACT FROM AUTHOR]

The complex ceramic core used for hollow turbine blades requires high porosity and flexural strength. This work combined vat photopolymerization 3D printing with sacrificial template method to prepare Al2O3 ceramic cores with strip‐shaped pores using polyamide 6 (PA6) fibers as templates. When the porosity was greater than 30%, the maximum flexural strength reached up to 110.48 MPa. The sacrificial templating method improved the porosity of Al2O3 ceramic cores, forming an internal porous structure that combined strip‐shaped large pores with irregularly shaped small pores. The influences of PA6 fiber content and diameter on the shrinkage, porosity, microstructure, and comprehensive properties of alumina ceramic cores were studied, revealing the mechanism of the coexistence of high porosity and high strength. [ABSTRACT FROM AUTHOR]

Today, controlling the photopolymerization process during the 3D printing in vat photopolymerization is a key challenge. In this work, it is shown that using a relatively limited set of parameter, it is possible to estimate key factors involved in such process. On the basis of 16 formulations containing different concentrations of photoinitiator and UV filter, attempt was made to rationalize the photonic parameters used in the 3D printing process, that is, the depth of penetration Dp and the critical energy Ec. It is shown that the experimental Dp values can be correlated with calculated ones from Bouguer–Beer–Lambert law. Real‐time Fourier‐transform infrared spectroscopy (RT‐FTIR) experiments were performed under similar conditions as in 3D printing. The conversion profiles were used to estimate the Ec values. The limits of this approach was discussed as a function of the UV filter concentration. Finally, the RT‐FTIR curves are exploited to predict the in‐depth conversion of the different 3D printed layers and compared to experimental results obtained by confocal Raman microscopy. [ABSTRACT FROM AUTHOR]

Additive manufacturing is the state‐of‐the‐art method for producing complex ceramic parts. For cellular materials, the freedom of design is particularly advantageous, as pore networks and shapes can be tailored. Herein, the direct printing of complex parts with high porosity using the cost‐effective manufacturing method of Liquid Crystal Display‐based stereolithography on low‐cost printers is determined. It is investigated how the architecture of the alumina Kelvin cells topology, their fabrication process, the printing parameters, and the microstructure affect the accuracy and mechanical properties of the printed samples. A notable reduction to a strut thickness of Kelvin cells down to 0.20 mm is achieved corresponding to a reduction of 1.5 compared with the state‐of‐the‐art literature (min. 0.35 mm). Ultrahigh porosities between 89.5% and 97.2% and a maximum compressive strength of 1.84 ± 0.17 MPa are reached due to the dense struts of the structure. Low‐cost and simple vat ceramic photopolymerization with high accuracy printing proves to be a promising candidate for the rapid and cost‐effective fabrication of highly porous and complex ceramic structures. [ABSTRACT FROM AUTHOR]

The acrylates with oligomers and monomers from (partially) bio‐based feedstock become available at (semi‐)industrial scale, which can be processed through photochemical crosslinking for applications in coatings, additive manufacturing, electronics, or inks. Although fossil‐ and bio‐based acrylates may have a similar chemical composition, it requires good understanding of processing and structure–property relationships as minor changes in microstructure may strongly alter the performance. A comparative study on mechanical properties and chemical structure of bio‐ and fossil‐based acrylates with different functionalities and backbone structures reveals higher ductility of bio‐based acrylates, in relation with a more complex organization of the intrinsic molecular structure. The latter is confirmed by mechanical testing and visco‐elastic characteristics (dynamic mechanical analysis) yielding lower stiffness and higher dampening of bio‐based acrylates, in parallel with a lower glass transition temperature (differential scanning calorimetry). The complex molecular arrangements include a nanoscale morphology with ordered structure (X‐ray diffraction), conformational changes (infrared spectroscopy), and a residual high‐molecular weight fraction (size exclusion chromatography). The visco‐elastic calculations indicate only 4% to 5% lower crosslinking density and around 10% higher mean molar mass of the polymer chains segments between chemical crosslinks and trapped chain entanglements, which explain the unique structure and performance of bio‐based acrylates. [ABSTRACT FROM AUTHOR]

In the current study, a novel radical‐induced cationic frontal polymerization (RICFP) concept capable of rapid curing at room temperature via visible light irradiation is represented. Initially, the optimal formulation, which can be most effectively cured with visible light irradiation, is determined based on thickness, hardness, curing speed, and mechanical properties using FT‐IR, DSC, TGA, and flexural test methods. Subsequently, the viability of the method is illustrated by fabricating glass fiber‐reinforced composites through the hand lay‐up technique, employing the optimized formulation and glass fibers in various forms (chopped strand mat and biaxial). Mechanical properties of the obtained composites, including bending, tensile, and shear tests, are carried out according to relevant international standards and compared with reference composites thermally cured with amine‐based hardener by conventional method. [ABSTRACT FROM AUTHOR]

Polydiacetylene (PDA) is a kind of photopolymerizable polymer, which exhibits a unique color transition in response to external stimuli such as heat, pH, and solvent. PDAs are attractive as eye‐detection stimulus sensors with excellent time performance; however, the sensitivity of PDAs should be improved. Considering the biological membrane‐like structure of diacetylene (DA) vesicles, their modification by incorporating membrane lipids (e.g., diacylphosphocholine, PC) can be used to control the membrane fluidity, and consequently molecular ordering of DAs in the vesicle. Inspired by biological membrane systems, lipid vesicles are employed as platforms to generate PDA, and essential factors that influence the sensitivity of PDA are investigated. By lowering the polymerization temperature, the generation of PDA becomes slower, while the sensitivity improves. By adding PCs at the molar ratio of lipid:DA = 1:1, the sensitivity of PDA can be varied: the PCs with lower phase transition temperatures (Tm) made PDA insensitive, while the PCs with higher Tm improved the sensitivity as compared to pure poly(PCDA). It is concluded that the photopolymerization of DAs with a lower membrane fluidity induces highly sensitive PDA, while the photopolymerization of DAs with a higher membrane fluidity induces insensitive PDA with robustness toward stimuli. [ABSTRACT FROM AUTHOR]

Currently, most photoredox catalysis polymerization systems are limited by high excitation power, long polymerization time, or the requirement of electron donors due to the precise design of efficient photocatalysts still poses a great challenge. Herein, we propose a new approach: the creation of efficient photocatalysts having low ground state oxidation potentials and high excited state energy levels, along with through‐space charge transfer (TSCT) induced intersystem crossing (ISC) properties. A cabazole‐naphthalimide (NI) dyad (NI‐1) characterized by long triplet excited state lifetime (τT=62 μs), satisfactory ISC efficiency (ΦΔ=54.3 %) and powerful reduction capacity [Singlet: E1/2 (PC+1/*PC)=−1.93 eV, Triplet: E1/2 (PC+1/*PC)=−0.84 eV] was obtained. An efficient and rapid polymerization (83 % conversion of 1 mM monomer in 30 s) was observed under the conditions of without electron donor, low excitation power (10 mW cm−2) and low catalyst (NI‐1) loading (<50 μM). In contrast, the conversion rate was lower at 29 % when the reference catalyst (NI‐4) was used for photopolymerization under the same conditions, demonstrating the advantage of the TSCT photocatalyst. Finally, the TSCT material was used as a photocatalyst in practical lithography for the first time, achieving pattern resolutions of up to 10 μm. [ABSTRACT FROM AUTHOR]

Creatures, such as Venus flytrap and hummingbirds, capable of rapid predation through snap‐through transition, provide paradigms for the design of soft actuators and robots with fast actions. However, these artificial "snappers" usually need contact stimulations to trigger the flipping. Reported here is a constrained anisotropic poly(N‐isopropylacrylamide) hydrogel showing fast snapping upon light stimulation. This hydrogel is prepared by flow‐induced orientation of nanosheets (NSs) within a rectangular tube. The precursor containing gold nanoparticles is immediately exposed to UV light for photopolymerization to fix the ordered structure of NSs. Two ends of the slender gel are clamped to form a buckle with bistability nature, which snaps to the other side upon laser irradiation. Systematic experiments are conducted to investigate the influences of power intensity and irradiation angle of the laser, as well as thickness and buckle height of the gel, on the snapping behaviors. The fast snapping is further used to kick a plastic bead and control the switch state. Furthermore, synergetic or oscillated snapping of the gel with two buckles of opposite directions is realized by inclined irradiation of a laser or horizontal irradiation with two lasers, respectively. Such light‐steered snapping of hydrogels should merit designing soft robots, energy harvests, etc. [ABSTRACT FROM AUTHOR]

In the field of wound healing treatment, the development of new materials is essential to cover multiple functions, such as acceleration of the healing process, prevention of infection and response to stimuli, especially if they present lower costs or are easier to manufacture. These properties are of great importance to prompt skin cicatrization. In this work, new multifunctional skin dressings for wound healing and infection prevention are developed based on new hydrogel materials. The dressings are produced via a straightforward and environmentally friendly one‐pot photopolymerization manufacturing process utilizing vitamin B2 aqueous solutions as sensitizer, and energy‐efficient blue light sources. These dressings exhibit a high swelling capacity, pH and temperature responsiveness, biocompatibility, antimicrobial activity in the absence of conventional antibiotics, and are capable of promoting wound healing. The formulation is based on the combination of three monomers: 2‐((methacryloyloxy)ethyl)trimethylammonium chloride, methacrylic acid and N‐vinyl caprolactam. Collagen, hyaluronic acid, and essential oil of hop are added to enhance antimicrobial properties and stimulate regenerative cellular processes. In vivo experiments have demonstrated that pristine dressings are superior in promoting collagen and fibroblast regeneration and accelerating cicatrization as compared to dressings containing natural products. The dressing embedded with hop also displayed antimicrobial characteristics. The preparation and testing of these new efficient wound dressings are described. This study is distinctive in its integration of environmentally conscious manufacturing techniques with innovative material formulations, resulting in superior wound dressings that are both cost‐effective and highly functional. By achieving enhanced healing and infection prevention without the employment of conventional antibiotics, this work represents a substantial advancement in sustainable and effective wound care management. [ABSTRACT FROM AUTHOR]

Radiation curing is an excellent option for the economical implementation of coatings while simultaneously producing technically advanced products. Nevertheless, the number of materials used is mainly limited to pure (meth)acrylate and epoxy systems. Polyisocyanurates could be an excellent addition to this range, especially due to their thermal and chemical stability. In this work, through the use of a transition metal‐based photocatalyst, as well as the use of 1,5‐diazabicyclo(4.3.0)non‐5‐en as a co‐catalyst, formulations are presented, which enable pure polyisocyanurates to be used in radiation‐based coating technology. Trimerization with this system using any primary isocyanates worked and consequently thus opened the possibility for aromatic and aliphatic polyisocyanurates. Using monofunctional isocyanates, the theoretical background of trimerization as well as the theoretical enthalpy is evaluated and the possibilities as well as the limitations for poly‐trimerization of polyisocyanurates are analyzed. Finally, photo‐induced catalytic poly‐trimerization of aliphatic isocyanates is used to obtain samples with a Tg in the range of 100 °C and onset of degradation above 400 °C. Thus, for the first time, a framework for the use of isocyanates in the field of photopolymerization and, in particular, in the field of radiation‐based coating of polyisocyanurates is provided for further development. [ABSTRACT FROM AUTHOR]

We report on concomitant photoinitiated polymerization‐induced macrophase and microphase separation strategies to produce hierarchically structured recyclable poly(n‐butyl acrylate) based elastomeric materials. The investigated crosslinker‐free formulations are composed of n‐butyl acrylate monomer and a UV photo‐initiator mixed with poly(methyl methacrylate)‐b‐poly(n‐butyl acrylate)‐poly(methyl methacrylate) ABA triblock copolymers. Two different pre‐synthesized copolymers are used to control the macrophase separation. One synthesized by nitroxide‐mediated radical polymerization (NMRP), and a second by anionic polymerization (AP). Essentially, NMRP route leads to copolymer with unsaturated chain ends, activated during UV photopolymerization. On the other hand, the copolymer synthesized by AP are chemically inert. That dissimilarity is also highlighted by time‐resolved FTIR and SAXS, performed to monitor respectively monomer conversion and nanostructure evolution during photopolymerization. The experimental data demonstrate that the reactivity of the triblock copolymer impacts drastically the polymerization kinetics and the self‐assembly processes. Finally, the rheological analysis shows that the produced materials present a solid‐like behavior at low frequencies despite a large PnBA content (i.e., 85 wt%). This property is associated to the phase segregation and to the sample hierarchical morphology. [ABSTRACT FROM AUTHOR]

Benzophenone and its derivatives are widely used as UV filters and UV‐ink photoinitiators. The photoinitiating properties of benzophenones depend on their degree of conjugation and delocalization within the molecule. By understanding how conjugation, delocalization, and different substituents affect these properties, benzophenone derivatives can be customized for specific applications. Using quantum mechanical calculations based on B3LYP/6‐311++G(d, p) density functional theory (DFT), chemical reactivity, stability, and photoinitiating capabilities of 4‐(4‐methylphenylthio)benzophenone are analyzed. This includes studying its physical and chemical properties in the gas phase, as well as its excited state electronic transitions, vibrational characteristics, and spectroscopic properties both in gas phase and in various solvents. The DFT‐computed infrared spectra match experimental results. The UV/Visible spectra shows absorption towards longer wavelengths due to extended delocalization of π‐electrons. In different solvents with varying polarity, the absorption spectra exhibit high‐intensity peaks, shift in excitation energy and wavelengths based on the polarity of the solvent. This knowledge allows for the development of novel initiators with customized light absorption, excited state lifetimes, and reaction selectivities, which can enhance processes like UV‐curing, photopolymerization, and other light‐driven reactions. [ABSTRACT FROM AUTHOR]

The emulsion photopolymerization of methyl methacrylate (MMA) using red light is reported. The synthesis of poly(methyl methacrylate) (PMMA) latexes is initiated by irradiation of a new, very efficient red‐absorbing methylene blue (MB)/sodium para‐toluenesulfinate (NapTS) system in the red region (660 nm). Visible, and especially red light penetrates the dispersed medium imposed by the emulsion process better than ultra‐violet photons (UVs). However, emulsion photopolymerizations require the development of fully water‐soluble initiating systems activable by red light, which is still hugely challenging because red photons are much less energetic, therefore generally lead to less efficient photochemical processes. The influence of the surfactant concentration and the solids content is examined over particle sizes and polymerization kinetics. The polymerizations work for solids contents between 10 and 25 wt%, with narrowly distributed particles of average sizes ranging from 40 to 65 nm. Calculations of Mie scattering support the observation that at a given wavelength the larger the particles the lower the penetration. All latexes obtained are slightly blue, which are traced to the regeneration of MB when the latexes are exposed to dioxygen. The dye regeneration enables the reactivation of the photopolymerization process. [ABSTRACT FROM AUTHOR]

The additive manufacturing (AM) industry increasingly looks to differentiate itself by utilizing materials and processes that are green, clean, and sustainable. Biopolymers, bio‐sourced raw materials and light weighting of parts 3D printed with photopolymer resins each represent critical directions for the future of AM. Here, we report a series of bio‐based composite resins with soybean oil derivatives, up to 20% by weight of surface‐methacrylated micro‐crystalline cellulose (MCC) and 60% total bio‐based content for vat photopolymerization based additive manufacturing. The ultimate tensile strengths of the materials were found to increase up to 3X, the Young's moduli increased up to 10X, and the glass transition temperature increased by 11.3°C when compared to the neat resin without surface‐methacrylated MCC as a filler. Working curves and shrinkage factors were used to demonstrate how the surface‐methacrylated MCC causes changes in the dimensions of printed parts, to facilitate development of optimized print parameters based on the UV intensity of the 3D printer being used. These results will allow further development of commercial 3D printable resins with a high concentration of bio‐based fillers that print well and perform on par with conventional resins. [ABSTRACT FROM AUTHOR]

Light‐mediated 3D printing techniques have gained significant interest due to the inherent advantages of light as external stimuli, including spatiotemporal control and easy access. As 3D printing processes require rapid polymerization, free radical or cationic polymerization methods are used. However, these polymerization reactions are limited to the production of materials with properties that cannot be chemically altered post‐printing. In this work, a rapid, open‐to‐air photo‐controlled cationic reversible addition‐fragmentation chain‐transfer polymerization of vinyl ethers is demonstrated in the presence of a three‐component photoinitiating system comprising a photosensitizer, electron donor, and acceptor as co‐initiators under the irradiation with blue light. The polymerization mechanism shows rapid kinetics and controlled, living polymerization characteristics. Trithiocarbonate chain ends of poly(isobutyl vinyl ethers) are reactivated to produce block copolymers with cyclohexyl vinyl ethers. The rapid kinetics and water tolerance of the reported system enable the 3D printing of polymeric solids under ambient (e.g., room temperature and open to air) conditions, followed by the effective reactivation of trithiocarbonate chain ends to post‐synthetically modify the object with an acrylate‐based fluorescent monomer via a controlled radical polymerization strategy. [ABSTRACT FROM AUTHOR]

Nowadays, photopolymerization has spanned across all academic and industrial applications due to its appealing features such as energy saving, environmentally‐friendly polymerization conditions, high monomer conversions, rapid polymerization kinetics and so on. Photoinitiator (PI), as a crucial component of the photoinitiating system (PIS) are capable of interacting with light efficiently, enabling to generate initiating species in mono or multicomponent systems. In this work, 13 phenothiazine‐based oxime esters (OXEs) (never reported before) were synthesized and their photoinitiation abilities for the free radical photopolymerization (FRP) of acrylates were examined upon irradiation with LED@405 nm. Parallel to their photochemical reactivities, their abilities to initiate thermal polymerization processes were also investigated. Finally, these OXEs exhibited excellent photo/thermal initiation performances, demonstrating their dual initiation properties. Phenothiazine‐based oxime esters can be used as PIs in 3D printing as well as thermal initiator in the manufacturing of carbon fiber composites. [ABSTRACT FROM AUTHOR]

Stimuli‐responsive materials have recently gained significant attention in the field of soft robotics, sensors, and biomimetic devices. The most facile way for the fabrication of such materials remains to endow bilayer structures which are fabricated with the combination of active and passive layers. Although, easily fabricated, these structures suffer from the generation of stress points between connection areas. In this work we develop a method to create a thin film with controlled cross‐link variation across its thickness. The cross‐link gradient is achieved through polymerization induced diffusion of dithiol molecules in thiol‐ene network. As a result, the film exhibits bending deformation upon illumination with light or exposure to a chemical solvent, thereby demonstrating dual responsiveness. Light actuation of the film is achieved via photothermal effects due to the incorporation of dye into the system which can absorb UV light and heat the network. While solvent induced actuation is due to anisotropic swelling. Furthermore, the straightforward fabrication procedure allows for the creation of more complex deformations by patterning the film using a photomask during photopolymerization. [ABSTRACT FROM AUTHOR]

4D printing has emerged as a powerful strategy capable of revolutionizing additive manufacturing by enabling objects to dynamically transform overtime on demand. Despite significant progress, the full potential remains unrealized, particularly in the utilization of dynamic covalent chemistry. This study introduces a new approach using a multifunctional cross‐linker with alkoxyamine functionalities for 4D printing. Digital light processing (DLP) is employed for high‐resolution printing of complex objects. Leveraging alkoxyamine bonds' dynamic and living characteristics, the printed structures can be further modified through nitroxide‐mediated polymerization (NMP) using styrene and nitroxide exchange reactions (NER). The resulting "living" printed structures exhibit the unique ability to undergo both "growth" and "degrowth", dynamically adapting their size as well as the reduced Young's Modulus across a wide range (770 kPa–1.2 GPa). The chain extension by NMP and softening by NER are carefully characterized by IR and EPR spectroscopy. The presented approach opens avenues for the development of 4D printed structures with complex adaptive systems, showcasing enormous potential in a wide range of fields. [ABSTRACT FROM AUTHOR]

Additive manufacturing (AM) of copper through laser‐based processes poses challenges, primarily attributed to the high thermal conductivity and low laser absorptivity of copper powder or wire as the feedstock. Although the use of copper salts in vat photopolymerization‐based AM techniques has garnered recent attention, achieving micro‐architected copper with high conductivity and density has remained elusive. In this study, we present a facile and efficient process to create complex 3D micro‐architected copper structures with superior electrical conductivity and hardness. The process entails the formulation of an ion‐exchangeable photoresin, followed by the utilization of digital light processing (DLP) printing to sculpt 3D hydrogel scaffolds, which were transformed into Cu2+‐chelated polymer frameworks (Cu‐CPFs) with a high loading of Cu2+ ions through ion exchange, followed by debinding and sintering, results in the transformation of Cu‐CPFs into miniaturized copper architectures. This methodology represents an efficient pathway for the creation of intricate micro‐architected 3D metal structures. [ABSTRACT FROM AUTHOR]

The development of visible light‐regulated polymerizations for precision synthesis of polymers has drawn considerable attention in the past years. In this study, an ancient dye, indigo, is successfully identified as a new and efficient photoacid catalyst, which can readily promote the ring‐opening polymerization of lactones under visible light irradiation in a well‐controlled manner, affording the desired polyester products with predictable molecular weights and narrow dispersity. The enhanced acidity of indigos by excitation is crucial to the H‐bonding activation of the lactone monomers. Chain extension and block copolymer synthesis are also demonstrated with this method. [ABSTRACT FROM AUTHOR]

Photopolymerizations have garnered significant attention in polymer science due to their low polymerization temperature, high production efficiency, environmental friendliness, and spatial controllability. Despite these merits, the poor penetration and severe chemical damage from ultraviolet/visible (UV/Vis) light resources pose significant barriers to their success in conventional photopolymerizations. A recent breakthrough involving the utilization of near‐infrared (NIR) laser with long wavelength has been exploited for diverse applications. With the combination of a NIR photosensitizer (PS), NIR‐induced photopolymerizations have been successfully developed to alleviate the challenges in conventional methods. The enhancement of penetration depth and safety of NIR‐induced photopolymerizations can contribute significantly to improving the efficiency of polymerization for production of intricate structures across various scales. In this concept, the typical types of PSs and polymerization mechanisms (PMs) within the NIR‐induced photopolymerization systems have been classified in detail. Additionally, the applications of various polymers achieved by NIR‐induced photopolymerizations are summarized. Furthermore, research directions and future challenges of this field are also discussed comprehensively. [ABSTRACT FROM AUTHOR]