Article
Materials Science, Multidisciplinary
Roland Taschner, Robert Liska, Patrick Knaack
Summary: Iodonium antimonates and borates are widely used initiators in polymerization, while cyanide-ligated borane B2 is a new type of initiator with high reactivity and cost-effectiveness.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Materials Science, Multidisciplinary
Matteo Turani, Andrea Baggio, Valentina Casalegno, Milena Salvo, Marco Sangermano
Summary: UV-initiated cationic frontal polymerization is used as a fast and low-temperature technique to produce epoxy-based adhesives, with critical parameters such as joint thickness, adherends nature, and temperature influencing the final joint strength. The thermal properties of the epoxy formulation and joint strengths are studied to show comparable performance to traditional energy-intensive techniques.
MACROMOLECULAR MATERIALS AND ENGINEERING
(2021)
Article
Chemistry, Applied
Yangyang Xin, Shizhuo Xiao, Yulian Pang, Yingquan Zou
Summary: This paper investigates the use of Near-Infrared sensitizer induced Radical Induced Cationic frontal polymerization (RICFP) in vinyl ethers and epoxides. It was found that vinyl ethers exhibited higher reactivity and conversion rates compared to other cationic polymerizable monomers. The study also explored the use of a three-component system with NIR sensitizer, iodonium salt, and thermal initiator in RICFP.
PROGRESS IN ORGANIC COATINGS
(2021)
Article
Polymer Science
Roland Taschner, Patrick Knaack, Robert Liska
Summary: Cationic polymerization is a powerful tool for various applications such as adhesive, coating, composite, and bulk material production. Epoxy-based systems are commonly used due to their high reactivity and versatility. The introduction of radical induced cationic frontal polymerization (RICFP) has provided a more efficient pathway for curing epoxides, with bismuth-based initiator systems showing advantages in terms of pot life and reactivity.
JOURNAL OF POLYMER SCIENCE
(2021)
Article
Polymer Science
Xing Huang, Mengquan Shi, Haoqi Zhai, Yuxi Zhang, Yunlong Zhang, Yuxia Zhao
Summary: In this study, nitrogen-doped carbon dots with certain water solubility were developed for photopolymerization applications. The carbon dots exhibited excellent visible light photoinitiation activity and biocompatibility, making them promising for 3D printing and biomedicine. CD-2, with a higher nitrogen content and mainly in pyridinic and pyrrolic forms, showed enhanced photoinitiation efficiency compared to CD-1.
Article
Optics
Suwat Romphosri, Phyu Sin Oo, Pornpawee Karanyasopon, Rakchart Traiphhol, Tanant Waritanant
Summary: It is found that Michler's ketone (MK) can be used for two-photon polymerization under near-infrared irradiation, and it has a large absorption cross-section, proving MK as a promising photoinitiator for low-cost two-photon polymerization.
APPLIED PHYSICS B-LASERS AND OPTICS
(2022)
Article
Polymer Science
Fatima Hammoud, Julie Kirschner, Meline Carre, Wolfgang Paulus, Anna-Maria Cristadoro, Michael Schmitt, Jacques Lalevee
Summary: Frontal polymerization (FP) has attracted increasing interest for the polymerization of thick materials with high fillers content. This study reports recent advances in controllable and predictive behavior for photoinduced frontal photopolymerization using tert-butyl peroxybenzoate (Luperox-P) as a thermal initiator. The experiments investigate various factors and their influence on photoinduced frontal polymerization, resulting in a statistical design of experiments.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Article
Nanoscience & Nanotechnology
Brecklyn R. Groce, Emma E. Lane, Daniel P. Gary, Douglas T. Ngo, Dylan T. Ngo, Fahima Shaon, Jorge A. Belgodere, John A. Pojman
Summary: The addition of fillers to resin systems can improve the mechanical properties and lower the cost. In this study, various clays and fumed silica were added to epoxies and vinyl ethers for radical-induced cationic frontal polymerization. The clays reduced the front velocity, possibly due to chemical effects and water content. Mechanical properties, thermal properties, and filler dispersion were investigated. Acid-treated montmorillonite K10 was found to polymerize vinyl ether systems without an initiator, resulting in a short pot life.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Polymer Science
Daniele Maugeri, Marco Sangermano, Yves Leterrier
Summary: Two different interpenetrating phase composites were produced using a radical photoinduced cationic frontal polymerization process. The influence of different initiators on the frontal polymerization features was systematically evaluated. Complete conversion of the epoxy resin was achieved within a short time under proper concentration, but led to high temperature and material degradation.
POLYMER INTERNATIONAL
(2021)
Article
Polymer Science
Filip Petko, Mariusz Galek, Emilia Hola, Roman Popielarz, Joanna Ortyl
Summary: This paper presents a novel method for synthesizing benzylidene iodonium salts as photoinitiators and investigates their properties, showing efficient decomposition under UV to visible light and potential application in 3D printing.
Article
Polymer Science
Filip Petko, Andrzej Swiezy, Magdalena Jankowska, Pawel Stalmach, Joanna Ortyl
Summary: In this article, a new group of cationic photoinitiators is introduced and their photophysical properties and photoinitiating activity are analyzed with respect to the arrangement of electron-donating substituents in the coumarin chromophore. The authors observed two patterns of D-pi-A structure in the five new coumarin-based iodonium salts, which differ in the strength of the push-pull effect that determines their properties. These photoinitiators show excellent activity at 365 nm, 405 nm, and 415 nm and exhibit increased activity at elevated temperatures due to thermal reactions with monomers. This photo-thermal initiating activity makes them excellent photoinitiators for nanocomposite DLP 3D-VAT printing, overcoming scattering and shadowing problems.
Article
Materials Science, Multidisciplinary
Roland Taschner, Thomas Koch, Raffael Wolff, Jurgen Stampfl, Robert Liska, Patrick Knaack
Summary: Sulfonium hexafluorophosphates and perfluorinated tetraphenylborates are commonly used initiators in cationic photopolymerization and have been applied in 3D-printing at high temperatures. The cyanide-ligated borane-based photoinitiator B2 shows higher reactivity and lower cost compared to other borates. B2 exhibits excellent performance in epoxy monomer conversions at a wide range of temperatures. In addition, B2-based formulations are stable and can be sensitized by anthracene derivatives. B2 also outperforms existing sulfonium initiators in terms of layer quality and coloration in hot lithography.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Polymer Science
Loic Buchon, Jean-Michel Becht, Laurent Rubatat, Wei Wang, Hua Wei, Pu Xiao, Jacques Lalevee
Summary: This research synthesized and characterized four potential phosphine oxide photoinitiators and evaluated their efficiency in photopolymerization at 405 nm wavelength. Two of the obtained photoinitiators showed better performance than the widely used commercial photoinitiator. Additionally, one of the synthesized photoinitiators was successfully used in 3D printing of thermoplastics and exhibited lower cytotoxicity compared to the benchmark structure.
JOURNAL OF APPLIED POLYMER SCIENCE
(2023)
Review
Chemistry, Multidisciplinary
Zilong Wu, Cyrille Boyer
Summary: Near-infrared (NIR) light-induced reversible deactivation radical polymerization (NIR-RDRP) is an effective technique for preparing functional polymer materials using light energy. This review comprehensively summarizes the mechanisms and applications of NIR-RDRP systems.
Article
Polymer Science
James B. Young, Jared Bowman, Cabell B. Eades, Alexander J. Wong, Brent S. Sumerlin
Summary: Controlled radical polymerization techniques allow for the synthesis of polymers with specific molecular weights and architectures. In this study, the role of light in triggering thermal depolymerization of polymers synthesized through reversible-addition-fragmentation chain-transfer (RAFT) polymerization was investigated. By targeting specific electronic transitions, the depolymerization efficiency was enhanced.
Article
Polymer Science
Lorenzo Pezzana, Giuseppe Melilli, Nathanael Guigo, Nicolas Sbirrazzuoli, Marco Sangermano
Summary: This article investigates the use of furfuryl glycidyl ether (FGE) as a monomer to design a two-step cured coating. Linear polymer chains are produced using cationic UV technique, and the UV reactivity of FGE is evaluated using real-time Fourier Transform Infrared Spectroscopy (FTIR). After a thermal treatment, the formation of cross-links in the UV-irradiated linear chains is confirmed using various techniques.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Article
Materials Science, Multidisciplinary
Elisabeth Rossegger, Rita Hoeller, Katja HrbiniC, Marco Sangermano, Thomas Griesser, Sandra Schloegl
Summary: Magnetoresponsive polymers are important materials in the design of soft actuators, allowing for controlled movement through an external magnetic field. By incorporating magnetoresponsiveness into photocurable resins, personalized and complex structures can be created and driven by a magnetic field using 3D printing technology.
ADVANCED ENGINEERING MATERIALS
(2023)
Article
Polymer Science
Marco Sangermano, Antonio Grieco, Camilla Noe, Giancarlo Rizza
Summary: The development of a novel technique using photopolymerization to obtain PDMS membranes provides a fast and simple solution to the worldwide challenge of oil removal from water. The high reactivity of the acrylated PDMS formulation in photo-induced free radical polymerization is evaluated using differential scanning photo-calorimetry. Two types of membranes, dense or porous, are developed and studied, with the porous membranes obtained using an environmentally friendly sodium chloride template. The hydrophobic/oleophilic nature of PDMS allows the UV-cured membranes to selectively remove the target oil, dodecane, from water. The dodecane sorption capability of both membranes is investigated and compared, and the membranes can be easily reused by compressing them to recover the adsorbed oil. These PDMS sorbents exhibit high mechanical stability after five adsorption/desorption cycles.
MACROMOLECULAR CHEMISTRY AND PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Anna Widera, Riccardo Conti, Andrea Cosola, Ashling Fah, Debora Thony, Marco Sangermano, Joelle Levalois-Grutzmacher, Hansjoerg Grutzmacher
Summary: A N-hydroxy succinimide (NHS) ester substituted bis(acyl)phosphane oxide (ACTIVE-BAPO) was synthesized and used for one-step ligation with substrates containing primary amino groups. This led to the formation of new molecular and polymeric photoinitiators. The PAMAM BAPOs exhibited high efficiency as photoinitiators for free radical polymerization. Interestingly, they also acted as crosslinking agents without additional additives, resulting in thermosetting networks with varying degrees of crosslinking and swelling capabilities in water.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Optics
Andrea Baggio, Matteo Turani, Massimo Olivero, Milena Salvo, Diego Pugliese, Marco Sangermano
Summary: A new system is developed to detect hydrocarbons using optical fiber distributed sensing. The system utilizes a custom-designed optical fiber with silica core and thin silicone cladding, providing quick and selective absorption of oil products and insensitivity to water. By detecting Rayleigh backscattering, the system demonstrates a rapid response to high refractive index hydrocarbons, with a response time of approximately 1 s. Furthermore, in its high-resolution version, the system can accurately locate leakages with an accuracy of 14 cm.
OPTICS AND LASER TECHNOLOGY
(2023)
Article
Polymer Science
Matteo Bergoglio, David Reisinger, Sandra Schloegl, Thomas Griesser, Marco Sangermano
Summary: In this study, a bio-based solvent-free vitrimer was successfully synthesized using epoxidized castor oil (ECO) through a UV-curing process. Real-time Fourier-transformed infrared spectroscopy and photo-DSC were used to monitor the UV-curing process. The UV-cured polymer networks exhibited thermo-activated bond exchange reactions due to the presence of a transesterification catalyst. The ECO-based vitrimer showed high thermal resistance and good mechanical properties, making it a promising starting point for sustainable vitrimers.
Article
Multidisciplinary Sciences
Sathiyaraj Subramaniyan, Matteo Bergoglio, Marco Sangermano, Minna Hakkarainen
Summary: In order to move towards a circular bioeconomy, a paradigm shift from traditional petroleum-based non-recyclable thermosets to biobased repeatedly recyclable materials is required. Two mechanically and chemically recyclable extended vanillin-derived epoxy thermosets were successfully fabricated by introducing Schiff-base/imine covalent dynamic bonds. These thermosets exhibited good thermal and mechanical properties, stability in common organic solvents, and the ability to be thermally reprocessed through compression molding. Furthermore, they could be rapidly and completely chemically recycled to water-soluble aldehydes and amines by imine hydrolysis in 0.1M HCl solution.
Article
Electrochemistry
M. Longo, M. Gandolfo, C. Francia, S. Bodoardo, M. Sangermano, J. Amici
Summary: This article presents a method of preparing efficient gel electrolytes using gelatin from cold water fish skin to address various challenges in the practical application of lithium-oxygen batteries. The gel polymer electrolytes obtained through this method demonstrate good thermal and mechanical properties, as well as excellent electrochemical stability and high ionic conductivities.
ELECTROCHIMICA ACTA
(2023)
Article
Polymer Science
Cristian Mendes-Felipe, Igor Isusi, Olga Gomez-Jimenez-Aberasturi, Soraya Prieto-Fernandez, Leire Ruiz-Rubio, Marco Sangermano, Jose Luis Vilas-Vilela
Summary: The substitution of fossil resources by biomass alternatives is gaining importance in the chemical and energy industries. Fats, oils, and their derived products are essential inputs due to their functional attributes, stable price, and sustainable nature. Acrylated vegetable oils are versatile materials with various applications, and this study investigates different catalysts for the acrylation process and explores a novel one-step method for direct acrylation of vegetable oils, which is more environmentally efficient. The study also examines the potential for 3D printing of complex structures using the synthesized biomass-derived monomer via digital light processing (DLP) 3D printing.
Article
Polymer Science
Matteo Bergoglio, Ziba Najmi, Andrea Cochis, Marta Miola, Enrica Verne, Marco Sangermano
Summary: This study presents a novel approach for fabricating bioactive glass reinforced scaffolds using 3D printing technology. The composite scaffold, made from a bio-based acrylate resin derived from soybean oil and a reactive diluent called isobornyl acrylate, showed improved mechanical behavior compared to traditional mould-synthetized samples. The addition of bioactive glass particles did not significantly affect the curing process or the cytocompatibility of the scaffold, but resulted in higher metabolic activity and increased cell attachment on the scaffold surfaces.
Article
Polymer Science
Julia Amici, Giorgio Banaudi, Mattia Longo, Matteo Gandolfo, Michael Zanon, Carlotta Francia, Silvia Bodoardo, Marco Sangermano
Summary: In this study, an innovative lithium protective membrane based on chitosan was prepared and applied to lithium-oxygen batteries. The membrane effectively reduced the problems caused by the reactivity of lithium metal anode and the oxidative environment. The protected lithium cells showed higher discharge capacity and longer cycling performance.
Article
Chemistry, Multidisciplinary
Anna Liguori, Eugenia Oliva, Marco Sangermano, Minna Hakkarainen
Summary: Four isosorbide-based photocurable resins were designed and their correlations with composition, chemical structure, DLP 3D printability, thermoset properties, and recyclability were investigated. The study revealed the significant impact of resin composition on printability and physical properties of the resulting thermosets. The research also highlighted the successful reprocessing or chemical recycling of ester-imine thermosets with preserved elastic modulus, emphasizing the role of ester functionality concentration in recycling.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Lazaros Papadopoulos, Lorenzo Pezzana, Natalia Maria Malitowski, Marco Sangermano, Dimitrios. N. N. Bikiaris, Tobias Robert
Summary: In the search for sustainable thermosets, research has been conducted on various polymer classes, including epoxy, benzoxazines, acryl-/methacrylates, etc. Itaconic acid-based unsaturated polyester resins are a particular group that can also be used as sustainable inks for additive manufacturing. This study synthesized a series of itaconic acid-based polyesters with different reactive diluent contents and evaluated their physicochemical properties and reactivity toward UV light. The same formulations were used for 3D printing and their thermomechanical properties were examined.
Article
Chemistry, Applied
Lorenzo Pezzana, Alice Emanuele, Raffaella Sesana, Cristiana Delprete, Eva Malmstrom, Mats Johansson, Marco Sangermano
Summary: The scientific community is actively researching bio-based derivatives to reduce the consumption of fossil-based materials and their environmental impact. Developing bio-based plastics is a significant challenge in achieving sustainability and a green economy. A study focused on using a bio-based monomer, isosorbide, for the production of bio-based resins used in coatings. They successfully functionalized isosorbide to introduce epoxy groups, which were then activated through UV radiation for cross-linking. The bio-based resin showed potential for UV-cationic curing, reaching conversion rates above 85%. Additionally, they added a bio-based filler, macadamia nutshell powder (MAC), to increase the surface hardness of the coating. The resulting coating with 30% MAC showed a significant increase in hardness compared to the pristine bio-based epoxy resin. Thermo-mechanical analysis revealed that the addition of MAC also increased the glass transition temperature (Tg) of the coating.
PROGRESS IN ORGANIC COATINGS
(2023)
Article
Chemistry, Multidisciplinary
Amandine L. Flourat, Lorenzo Pezzana, Sabrina Belgacem, Abdouramane Dosso, Marco Sangermano, Sami Fadlallah, Florent Allais
Summary: In this study, tunable bis-allylated compounds were efficiently synthesized from cellulose-derived levoglucosenone via a chemo-enzymatic pathway, and then polymerized through photocuring, resulting in thermosets suitable for 3D printing.
